Ligand K-edge X-ray absorption spectroscopy and DFT calculations on [Fe3S4]0,+ clusters: delocalization, redox, and effect of the protein environment

Ligand K-edge XAS of an [Fe3S4]0 model complex is reported. The pre-edge can be resolved into contributions from the í2Ssulfide, í3Ssulfide, and Sthiolate ligands. The average ligand-metal bond covalencies obtained from these pre-edges are further distributed between Fe3+ and Fe2.5+ components using DFT calculations. The bridging ligand covalency in the [Fe2S2]+ subsite of the [Fe3S4]0 cluster is found to be significantly lower than its value in a reduced [Fe2S2] cluster (38% vs 61%, respectively). This lowered bridging ligand covalency reduces the superexchange coupling parameter J relative to its value in a reduced [Fe2S2]+ site (-146 cm-1 vs -360 cm-1, respectively). This decrease in J, along with estimates of the double exchange parameter B and vibronic coupling parameter ì2/k-, leads to an S ) 2 delocalized ground state in the [Fe3S4]0 cluster. The S K-edge XAS of the protein ferredoxin II (Fd II) from the D. gigas active site shows a decrease in covalency compared to the model complex, in the same oxidation state, which correlates with the number of H-bonding interactions to specific sulfur ligands present in the active site. The changes in ligand-metal bond covalencies upon redox compared with DFT calculations indicate that the redox reaction involves a two-electron change (one-electron ionization plus a spin change of a second electron) with significant electronic relaxation. The presence of the redox inactive Fe3+ center is found to decrease the barrier of the redox process in the [Fe3S4] cluster due to its strong antiferromagnetic coupling with the redox active Fe2S2 subsite.

Moluscos bivalves em Portugal: composição química e metais contaminantes

Dissertação para obtenção do Grau de Mestre em Tecnologia e Segurança Alimentar

Gd(III) chelates as NMR probes of protein-protein interactions. Case study: rubredoxin and cytochrome c3

Inorganic Chemistry 50(21):10600-7

Nitrite reduction by xanthine oxidase family enzymes: a new class of nitrite reductases

J Biol Inorg Chem (2011) 16:443–460 DOI 10.1007/s00775-010-0741-z

Artefacts induced on c-type haem proteins by electrode surfaces

J Biol Inorg Chem (2011) 16:209–215 DOI 10.1007/s00775-010-0717-z

Correlating EPR and X-ray structural analysis of arsenite-inhibited forms of aldehyde oxidoreductase

J Biol Inorg Chem (2007) 12:353–366 DOI 10.1007/s00775-006-0191-9

Kinetics studies of the superoxide-mediated electron transfer reactions between rubredoxin-type proteins and superoxide reductases

J Biol Inorg Chem (2006) 11: 433–444 DOI 10.1007/s00775-006-0090-0

X-ray crystal structure and EPR spectra of "arsenite-inhibited" Desulfovibriogigas aldehyde dehydrogenase: a member of the xanthine oxidase family

J. Am. Chem. Soc., 2004, 126 (28), pp 8614–8615 DOI: 10.1021/ja0490222

Estudos estruturais de interacções proteína-ligando: aldeído oxidorredutase e tripsina

Dissertação para obtenção do Grau de Mestre em Bioquímica Estrutural e Funcional

Hemolytic and urease activities in vibrios isolated from fresh and frozen oysters

INTRODUCTION: The present study aimed to survey the Vibrio microbiota of oysters (Crassostrea rhizophorae) obtained from restaurants in Fortaleza, State of Ceará, Brazil, and to identify virulence factors. METHODS: The isolated vibrios were submitted to biochemical identification and were tested for hemolytic and urease activities. RESULTS: The isolated strains belonged to 13 species, with predominance of Vibrio mimicus. Of the strain isolates only from fresh samples, 20.5% and 2.8% showed hemolytic and urease activities, respectively. CONCLUSIONS: The findings support the little-publicized claim that Vibrio species other than V. parahaemolyticus and V. vulnificus can represent a health risk to public health.

Elaboração de uma semi-conserva de pescado de água doce "Picles de Peixe". I. Tempo de cura, acidificação, textura e nível de sal

Neste trabalho são estudadas as condições para a correta combinação entre o tempo de cura, acidificação e nível de sal para produzir uma semi-conserva de pescado de de água doce acondicionada em vidro, utilizando o efeito da combinalção sal/ácido. As espécies utilizadas foram jaraqui (Semaprochilodus spp.), Curimatá (Prochilodus nigricans), Dourado (Brachyplastistoma flavicans) e Pirarucu (Arapaima gigas). Na salmora de cura prelimiar o tempo indicado para se obter uma melhor textura foi de 4 semanas, a acidificação até 4,5 foi alcançada na solução contendo 5% de ácido/100 gramas de pescado e o nível adequado de sal foi de 15% (p/v). Na salmora flavorizante a proporção de ácido foi de 1% (v/v) o que torna o produto de sabor agradável, sal na concentração de 2% (p/v) e a adição de 1% de condimentos.

A PESCA ARTESANAL NO BAIXO AMAZONAS: ANÁLISE MULTIVARIADA DA CAPTURA POR ESPÉCIE.

Dados sobre esforço e captura por espécie correspondentes à produção pesqueira desembarcada no porto de Santarém, no ano de 1993, foram submetidos a duas técnicas de análise multivariada: uma análise de fatores segundo o método de componentes principais e outra de co-variância conforme o modelo linear geral (GLM). Os resultados indicam que a atividade pesqueira na região está influenciada pelas características dos ciclos de vida das espécies-alvo, pelo ciclo hidrológico e condição climáticas de sistema, e ainda pelas preferências culturais e interesses econômicos do mercado consumidor. Os resultados indicam o direcionamento da atividade pesqueira para determinados grupos de espécies, e as diferentes variáveis incluídas no modelo permitiram uma explicação aproximada dos padrões desse direcionamento. Esses padrões são: (a) pesca de grandes bagres, alvo de pesca para a exportação (FATOR 1); (b) pesca de entre-safra do mapará (Hypophthalmusspp.) e da pescada (Plagioscionspp.), realizada nos lagos com um componente para exportação e outro para o consumo local (FATOR4); (c) pesca de peixes de escamas de hábitos sedentários e/ou migratórios, alvo da pesca comercial de pequena escala e de importância no mercado local (FATOR2, FATOR3 e FATOR5), que inclui pescarias importantes como a do tambaqui (Colossoma macropomum)e do pirarucu(Arapaima gigas)nos lagos, ou a do jaraqui (Semaprochilodusspp.) e pacu (Mylossomaspp. e Metynnisspp.) nos rios.

Report of the Shell Fish Commission of Maryland.

1

Experiências de adubação mineral e orgânica com Capim Kikuyu (Pennisetum clandestinum Hochst.)

Kikuio grass (Pennisetum clandestinum Hochst) is beyond any doubt, a pasture very important for farm animals; since its chemical composition is very similar to that of alfalfa, the present field trial was carried out; a randomized block design with 8 treatments was selected as follows: 1 N - P - K - Ca - Mg (complete manuring) 2 N - P - K - Ca----- (without Mg) 3 N - P - K-------Mg (without Ca) 4 ----P - K - Ca - Mg (without N) 5 N------K - Ca Mg (without P) 6 N - P - Ca - Mg (without K) 7 organic matter (without mineral fertilizers) 8 control Nitrogen was applied as NaN03 (topdressed) and as ammonium sulfate; P2O5 was given as superphosphate associated to bonemeal; K2O was applied as muriate, CaO as "sambaquis" (oyster shells); MgO was given as MgSO4 (topdressed). The source of organic matter was farmyard manure. As far yields are concerned the following observations were made: 1. treatment n. 7 was superior to all others; 2. considering the mineral fertilizers, good responses were due to N and P2O5; 3. the control yield was exceedingly poor, being inferior to all the others treatments; The chemical analyses revealed that: 1. the protein content decreased accordingly to this order: 7, 6, 5 and 1; treatment 4 (without N) gave the lowest protein content; 2. treatment n. 4 produced the highest fat content; treatment no. 7 ranked second; no. 8 gave the lowest fat content; 3. crude fiber: highest - treatment 7; lowest - 8; 4. ashes: the ashes content was higher in treatment 5; proprobably because the most abundant element in the ashes is K, the ash content of treatment 6 (no K) was very low; 5. non nitrogenous substances (determined by difference) - high in treatment 8 and low in treatment 7; 6. mineral elements in the ashes - the element omitted from a given treatment was very low in the grasses therein obtained; this shows the relative poverty of the soil in that element. As general remark the Authors suggest the use of farmyard manure in the fertilization of Kikuio grass; farmyard manure could probably substitute wither green manure or compost.

Distribuição geográfica da fauna e flora da Baía de Guanabara

The author studied, the horizontal and vertical distribution of most common part of the flora and fauna of the bay of Guanabara at Rio de Janeiro. In this paper the eulittoral, poly, meso and oligohaline regions were localised and studied; and the first chart of its distribution was presented (fig. 2). The salinity of superficial waters was established through determinations based on 30 trips inside the buy for collecting biological materials. Some often 409 determinations which were previous reported together with the present ones served for the eleboration of a salinity map of the bay of Guanabara (fig. 1). This map of fig. 2 shows the geographic locations of the water regions. EULITTORAL WATER REGIME — Fig. 3 shows the diagram scheme of fauna and flora of this regime. Sea water salinity 34/1.000, density mean 1.027, transparent greenish waters, sea coast with moderate bursting waves. Limpid sea shore with white sand, gneiss with the big barnacle Tetraclita squamosa var. stalactifera (Lam. Pilsbry. Vertical distributions: barna¬cles layers with a green region in which are present the oyster Ostrea pa-rasitica L., the barnacles Tetraclita, Chthamalus, Balanus tintinnabulum var. tintinnabulum (L.) e var. antillensis Pilsbry in connection with several mollusca and the sea beatle Isopoda Lygia sp. Covered by water and exposed to air by the tidal ritms, there is a stratum of brown animals that is the layer of mussels Mytilus perna L., with others brown and chestnut animals : the Crustacea Pachygrapsus, the little crab Porcellana sp., the stone crab Me-nippe nodifrons Stimpson, the sea stars Echinaster brasiliensis (Mull. & Tr.), Astropecten sp. and the sea anemones Actinia sp. Underneath and never visible there is a subtidal region with green tubular algae of genus Codium and amidst its bunches the sea urchin Lycthchinus variegatus (Agass.) walks and more deeply there are numerous sand-dollars Encope emarginata (Leske). The microplancton of this regime is Ceratiumplancton. POLYHALINE WATER REGIMB — Water almost sea water, but directly influenced by continental lands, with rock salts dissolved and in suspension. Salinity: 33 to 32/1.000. This waters endure the actions of the popular nicknamed «water of the hill» (as the waters of mesohaline and oligohaline regimes), becoming suddenly reddish during several hours. That pheno¬menon returns several times in the year and come with great mortality of fishes. In these waters, according to Dr. J. G. FARIA there are species of Protozoa : Peridinea, the Glenoidinium trochoideum St., followed by its satellites which he thinks that they are able to secret toxical substances which can slaughter some species of fishes. In these «waters of the hill» was found a species of Copepoda the Charlesia darwini. In August 1946 the west shore of the Guanabara was plenty of killed fishes occupying a area of 8 feet large by 3 nautical miles of lenght. The enclosure for catching fishes in the rivers mouthes presents in these periods mass dead fishes. The phenomenon of «waters of the hill» appears with the first rains after a period of long dryness. MESOHALINE WATER REGIME — Fig. 4 shows the the diagramm scheme. Salt or brackish water from 30 to 17/1.000 salinity, sometimes until 10/1.000. Turbid waters with mud in suspension, chestnut, claveyous waters; shore dirty black mud without waving bursting; the waters are warmer and shorner than those of the polihaline regime. Mangrove shore with the mangrove trees : Rhizophora mangle L., Avicennia sp., Laguncularia sp., and the »cotton tree of sea» Hibiscus sp. Fauna: the great land crab «guaimú» Cardisoma guanhumi Latr., ashore in dry firm land. There is the real land crab Ucides cordatus (L.) in wetting mud and in neigh¬ bourhood of the burrows of the fiddler-crabs of genus Uca. On stones and in the roots of the Rhizophora inhabits the brightly colored mangrove-tree-crab («aratu» Portuguese nickname) Goniopsis cruentata (Latreille) and the sparingly the big oyster Ostrea rhizophorae Guild. Lower is the region of barnacles Balanus amphitrite var. communis Darwin and var. niveus Darwin; Balanus tintinnabulum var. tintinnabulum (L.) doesn't grow in this brackish water; lower is the region of Pelecipoda with prepollency of Venus and Cytherea shell-fishes and the Panopeus mud crab; there are the sea lettuce Ulva and the Gastreropod Cerithium. The Paguridae Clibanarius which lives in the empty shells of Gasteropod molluscs, and the sessile ascidians Tethium plicatum (Lesuer) appears in some seasons. In the bottom there is a black argillous mud where the «one landed shrimps» Alpheus sp. is hidden. OLIGOHALINE WATER REGIME — The salinity is lower than 10/1.000. average 8/1.000. There are no barnacles and no sea-beetles Isopods of genus Lygia; on the hay of the shore there are several graminea. This brackish water pervades by mouthes of rivers and penetrates until about 3 kilometers river above. While there is some salt dissolved in water, there are some mud crabs of the genus Uca, Sesarma, Metasesarma and Chasmagnatus. The presence of floating green plants coming from the rivers in the waters of a region indicated the oligohaline waters, with low salt content because when the average of NaCl increases above 8/1.000 these plants die and become rusty colored.