Models of the Oxygen-Evolving Complex of Photosystem II

In the five chapters that follow, I delineate my efforts over the last five years to synthesize structurally and chemically relevant models of the Oxygen Evolving Complex (OEC) of Photosystem II. The OEC is nature’s only water oxidation catalyst, in that it forms the dioxygen in our atmosphere necessary for oxygenic life. Therefore understanding its structure and function is of deep fundamental interest and could provide design elements for artificial photosynthesis and manmade water oxidation catalysts. Synthetic endeavors towards OEC mimics have been an active area of research since the mid 1970s and have mutually evolved alongside biochemical and spectroscopic studies, affording ever-refined proposals for the structure of the OEC and the mechanism of water oxidation. This research has culminated in the most recent proposal: a low symmetry Mn₄CaO₅ cluster with a distorted Mn₃CaO₄ cubane bridged to a fourth, dangling Mn. To give context for how my graduate work fits into this rich history of OEC research, Chapter 1 provides a historical timeline of proposals for OEC structure, emphasizing the role that synthetic Mn and MnCa clusters have played, and ending with our Mn₃CaO₄ heterometallic cubane complexes.

In Chapter 2, the triarylbenzene ligand framework used throughout my work is introduced, and trinuclear clusters of Mn, Co, and Ni are discussed. The ligand scaffold consistently coordinates three metals in close proximity while leaving coordination sites open for further modification through ancillary ligand binding. The ligands coordinated could be varied, with a range of carboxylates and some less coordinating anions studied. These complexes’ structures, magnetic behavior, and redox properties are discussed.

Chapter 3 explores the redox chemistry of the trimanganese system more thoroughly in the presence of a fourth Mn equivalent, finding a range of oxidation states and oxide incorporation dependent on oxidant, solvent, and Mn salt. Oxidation states from Mn^II₄ to Mn^IIIMn^IV₃ were observed, with 1-4 O^2– ligands incorporated, modeling the photoactivation of the OEC. These complexes were studied by X-ray diffraction, EPR, XAS, magnetometry, and CV.

As Ca²⁺ is a necessary component of the OEC, Chapter 4 discusses synthetic strategies for making highly structurally accurate models of the OEC containing both Mn and Ca in the Mn₃CaO₄ cubane + dangling Mn geometry. Structural and electrochemical characterization of the first Mn₃CaO₄ heterometallic cubane complex— and comparison to an all-Mn Mn₄O₄ analog—suggests a role for Ca²⁺ in the OEC. Modification of the Mn₃CaO₄ system by ligand substitution affords low symmetry Mn₃CaO₄ complexes that are the most accurate models of the OEC to date.

Finally, in Chapter 5 the reactivity of the Mn₃CaO₄ cubane complexes toward O- atom transfer is discussed. The metal M strongly affects the reactivity. The mechanisms of O-atom transfer and water incorporation from and into Mn₄O₄ and Mn₄O₃ clusters, respectively, are studied through computation and ¹⁸O-labeling studies. The μ3-oxos of the Mn₄O₄ system prove fluxional, lending support for proposals of O^2– fluxionality within the OEC.

Measurement of the Polarization of the Cosmic Microwave Background with the BICEP2 and Keck Array Telescopes

Precision polarimetry of the cosmic microwave background (CMB) has become a mainstay of observational cosmology. The ΛCDM model predicts a polarization of the CMB at the level of a few μK, with a characteristic E-mode pattern. On small angular scales, a B-mode pattern arises from the gravitational lensing of E-mode power by the large scale structure of the universe. Inflationary gravitational waves (IGW) may be a source of B-mode power on large angular scales, and their relative contribution to primordial fluctuations is parameterized by a tensor-to-scalar ratio r. BICEP2 and Keck Array are a pair of CMB polarimeters at the South Pole designed and built for optimal sensitivity to the primordial B-mode peak around multipole l ~ 100. The BICEP2/Keck Array program intends to achieve a sensitivity to r ≥ 0.02. Auxiliary science goals include the study of gravitational lensing of E-mode into B-mode signal at medium angular scales and a high precision survey of Galactic polarization. These goals require low noise and tight control of systematics. We describe the design and calibration of the instrument. We also describe the analysis of the first three years of science data. BICEP2 observes a significant B-mode signal at 150 GHz in excess of the level predicted by the lensed-ΛCDM model, and Keck Array confirms the excess signal at > 5σ. We combine the maps from the two experiments to produce 150 GHz Q and U maps which have a depth of 57 nK deg (3.4 μK arcmin) over an effective area of 400 deg² for an equivalent survey weight of 248000 μK². We also show preliminary Keck Array 95 GHz maps. A joint analysis with the Planck collaboration reveals that much of BICEP2/Keck Array's observed 150 GHz signal at low l is more likely a Galactic dust foreground than a measurement of r. Marginalizing over dust and r, lensing B-modes are detected at 7.0σ significance.

Recolonisation of temporary streams and evolution of a degree of stability of the zoocenose [Translation from: Ecologia Mediterranea No.1 149-164, 1976]

When flow returns to a temporary stream a certain number of plant and animal species establish themselves more or less rapidly on the stream-bed constituting the initial phase of evolution of the re-population. This phase is essentially characterised by the ”awakening” of animal species that passed the dry season in a dormant state and by the development of the first unicellular algae that constitute the periphyton. Then they are succeeded by more or less stable animal groups and the structural complexity increases. The authors of the present study aim to analyse the dynamics of community succession from the return of water to the biotope until its drying up. It is attempted to determine the influence of the duration of flow on this evolution. This work is based on the analysis of population diversity with reference to its two complementary aspects, species richness and equitability. The River Destel which was studied for this project is situated in the Gorge of Ollioules near the town of Toulon.

A generalized treatment of the order-disorder transformation in alloys and its effects on their magnetic properties

A theory of the order-disorder transformation is developed in complete generality. The general theory is used to calculate long range order parameters, short range order parameters, energy, and phase diagrams for a face centered cubic binary alloy. The theoretical results are compared to the experimental determination of the copper-gold system, Values for the two adjustable parameters are obtained.

An explanation for the behavior of magnetic alloys is developed, Curie temperatures and magnetic moments of the first transition series elements and their alloys in both the ordered and disordered states are predicted. Experimental agreement is excellent in most cases. It is predicted that the state of order can effect the magnetic properties of an alloy to a considerable extent in alloys such as Ni₃Mn. The values of the adjustable parameter used to fix the level of the Curie temperature, and the adjustable parameter that expresses the effect of ordering on the Curie temperature are obtained.

I. Stokes flow past a thin screen. II. Viscous flows past porous bodies of finite size

Part I

The slow, viscous flow past a thin screen is analyzed based on Stokes equations. The problem is reduced to an associated electric potential problem as introduced by Roscoe. Alternatively, the problem is formulated in terms of a Stokeslet distribution, which turns out to be equivalent to the first approach.

Special interest is directed towards the solution of the Stokes flow past a circular annulus. A "Stokeslet" formulation is used in this analysis. The problem is finally reduced to solving a Fredholm integral equation of the second kind. Numerical data for the drag coefficient and the mean velocity through the hole of the annulus are obtained.

Stokes flow past a circular screen with numerous holes is also attempted by assuming a set of approximate boundary conditions. An "electric potential" formulation is used, and the problem is also reduced to solving a Fredholm integral equation of the second kind. Drag coefficient and mean velocity through the screen are computed.

Part II

The purpose of this investigation is to formulate correctly a set of boundary conditions to be prescribed at the interface between a viscous flow region and a porous medium so that the problem of a viscous flow past a porous body can be solved.

General macroscopic equations of motion for flow through porous media are first derived by averaging Stokes equations over a volume element of the medium. These equations, including viscous stresses for the description, are more general than Darcy's law. They reduce to Darcy's law when the Darcy number becomes extremely small.

The interface boundary conditions of the first kind are then formulated with respect to the general macroscopic equations applied within the porous region. An application of such equations and boundary conditions to a Poiseuille shear flow problem demonstrates that there usually exists a thin interface layer immediately inside the porous medium in which the tangential velocity varies exponentially and Darcy's law does not apply.

With Darcy's law assumed within the porous region, interface boundary conditions of the second kind are established which relate the flow variables across the interface layer. The primary feature is a jump condition on the tangential velocity, which is found to be directly proportional to the normal gradient of the tangential velocity immediately outside the porous medium. This is in agreement with the experimental results of Beavers, et al.

The derived boundary conditions are applied in the solutions of two other problems: (1) Viscous flow between a rotating solid cylinder and a stationary porous cylinder, and (2) Stokes flow past a porous sphere.

Optimization of the pyrolysis process for the production of a biomass derived reducing agent and hydrogen-rich gases

221 p.

Transgression in Carson McCullers The Ballad of the Sad Café

Este trabalho tem como objetivo principal discutir a obra The Ballad of the Sad Café, publicada em 1951, pela escritora norte-americana Carson McCullers, que abordou temas polêmicos, como a sexualidade, papéis sociais e suas respectivas e muitas vezes concomitantes transgressões. Em tal discussão serão analisadas as presenças do Gótico, do Grotesco e de outros elementos literários que se mostram eficazes ao lidarmos com a subversão dos valores patriarcais construídos socialmente. Como pontos cruciais deste trabalho, será traçado um paralelo entre a sociedade vitoriana e a sociedade do Sul norte-americano de meados do século XX, enfocando também a protagonista Miss Amelia Evans, que desafia o modelo da heroína gótica tradicional

An evaluation of the survival of Atlantic salmon (Salmo salar L.)fry stocked in eight streams in the North West of England.

Eight streams from the North West of England were stocked with Atlantic salmon (Salmo salar L.) fed fry at densities ranging from 1 to 4/m2 over a period of up to three years to evaluate survival to the end of the first an d second growing periods and hence assess the value of stocking as a management practice. Survival to the end of the first growin g period (mean duration of 108 days) was found to vary between 7.8 and 41.3% with a mean of 22% and CV of 0.44. Survival from the end of the first growing period to the end of the second growing period (mean duration of 384 days) ranged from 19.9 to 34.1% with a mean of 26.3% and CV of 0.21. Survival was found to be positively related to 0+ trout density (P < 0.05) and negatively related to altitude (P < 0.05). A comparison of the raw survival data (non standardised with respect to duration of experiments) with that from other studies in relation to stocking densities revealed a negative relationship between fry survival and stocking density (P < 0.05). Densities in excess of 5/m2 tended to result in lower levels of survival. Post stocking fry dispersal patterns were examined for the 1991 data. On average 86.7% of the number of fry surviving remained within the stocked zone by the end of the first growing period. With the exception of one stream there was little in the way of dispersal beyond the stocked zone. The dispersal pattern approximated to the normal distribution (P < 0.05). It was estimated that stocking can result in a net gain of fish to a river system compared with natural productivity, however the numerical significance of this gain and its cost effectiveness need to be determined on a river specific basis.

Review of the crevalle jacks, Caranx hippos complex (Teleostei: Carangidae), with a description of a new species from West Africa

The Caranx hippos species complex comprises three extant species: crevalle jack (Caranx hippos) (Linnaeus, 1766) from both the western and eastern Atlantic oceans; Pacific crevalle jack (Caranx caninus) Günther, 1868 from the eastern Pacific Ocean; and longfin crevalle jack (Caranx fischeri) new species, from the eastern Atlantic, including the Mediterranean Sea and Ascension Island. Adults of all three species are superficially similar with a black blotch on the lower half of the pectoral fin, a black spot on the upper margin of opercle, one or two pairs of enlarged symphyseal canines on the lower jaw, and a similar pattern of breast squamation. Each species has a different pattern of hyperostotic bone development and anal-fin color. The two sympatric eastern Atlantic species also differ from each other in number of dorsal-and anal-fin rays, and in large adults of C. fischeri the lobes of these fins are longer and the body is deeper. Caranx hippos from opposite sides of the Atlantic are virtually indistinguishable externally but differ consistently in the expression of hyperostosis of the first dorsalfin pterygiophore. The fossil species Caranx carangopsis Steindachner 1859 appears to have been based on composite material of Trachurus sp. and a fourth species of the Caranx hippos complex. Patterns of hyperostotic bone development are compared in the nine (of 15 total) species of Caranx sensu stricto that exhibit hyperostosis.

Age and growth of the estuarine dolphin (Sotalia guianensis) (Cetacea, Delphinidae) on the Paraná Coast, southern Brazil

Teeth of 71 estuarine dolphins (Sotalia guianensis) incidentally caught on the coast of Paraná State, southern Brazil, were used to estimate age. The oldest male and female dolphins were 29 and 30 years, respectively. The mean distance from the neonatal line to the end of the first growth layer group (GLG) was 622.4 ±19.1 μm (n=48). One or two accessory layers were observed between the neonatal line and the end of the first GLG. One of the accessory layers, which was not always present, was located at a mean of 248.9 ±32.6 μm (n=25) from the neonatal line, and its interpretation remains uncertain.The other layer, located at a mean of 419.6 ±44.6 μm (n=54) from the neonatal line, was always present and was first observed between 6.7 and 10.3 months of age. This accessory layer could be a record of weaning in this dolphin. Although no differences in age estimates were observed between teeth sectioned in the anterior-posterior and buccal-lingual planes, we recommend sectioning the teeth in the buccal-lingual plane in order to obtain on-center sections more easily. We also recommend not using teeth from the most anterior part of the mandibles for age estimation. The number of GLGs counted in those teeth was 50% less than the number of GLGs counted in the teeth from the median part of the mandible of the same animal. Although no significant difference (P>0.05) was found between the total lengths of adult male and female estuarine dolphins, we observed that males exhibited a second growth spurt around five years of age. This growth spurt would require that separate growth curves be calculated for the sexes. The asymptotic length (TL∞), k, and t0 obtained by the von Bertalanffy growth model were 177.3 cm, 0.66, and –1.23, respectively, for females and 159.6 cm, 2.02, and –0.38, respectively, for males up to five years, and 186.4 cm, 0.53 and –1.40, respectively, for males older than five years. The total weight (TW)/total length (TL) equations obtained for male and female estuarine dolphins were TW = 3.156 × 10−6 × TL 3.2836 (r=0.96), and TW = 8.974 × 10−5 × TL 2.6182 (r=0.95), respectively.

Age and growth of the swordfish (Xiphias gladius L.) in the waters around Taiwan determined from anal-fin rays

Age and growth of the swordfish (Xiphias gladius) in Taiwan waters was studied from counts of growth bands on cross sections of the second ray of the first anal fin. Data on lower jaw fork length and weight, and samples of the anal fin of male and female swordfish were collected from three offshore and coastal tuna longline fishing ports on a monthly basis between September 1997 and March 1999. In total, 685 anal fins were collected and 627 of them (293 males and 334 females) were aged successfully. The lower jaw fork lengths of the aged individuals ranged from 83.4 to 246.6 cm for the females and from 83.3 to 206 cm for the males. The radii of the fin rays and growth bands on the cross sections were measured under a dissecting microscope equipped with an image analysis system. Trends in the monthly marginal increment ratio indicated that growth bands formed once a year. Thus, the age of each fish was deter-mined from the number of visible growth bands. Two methods were used to estimate and compare the standard and the generalized von Bertalanffy growth parameters for both males and females. The nonlinear least square estimates of the generalized von Bertalanffy growth parameters in method II, in which a power function was used to describe the relationship between ray radius and LJFL, were recommended as most acceptable. There were significant differences in growth parameters between males and females. The growth parameters estimated for females were the following: asymptotic length (L∞) = 300.66 cm, growth coefficient (K) = 0.040/yr, age at zero length (t0) = –0.75 yr, and the fitted fourth parameter (m) = –0.785. The growth parameters estimated for males were the following: asymptotic length (L∞) = 213.05 cm, growth coefficient (K) = 0.086/yr, age at zero length (t0) = –0.626 yr, and the fitted fourth parameter (m) = –0.768.

Wadge Bank trawl fishery studies. Pt. 1. The effect of the 1928 to 1935 commercial trawling on the demersal stock

The demersal fish stock of Wadge Bank is one of the important fish resources for both Sri Lanka and India. Sivalingam and Medcof (1957) have given an account of its history, general features and relative productivity. According to records the total fishing effort on the bank had been fluctuating and very recently the number of boats operating on the bank has suddenly increased, and there is a possibility that still more will begin operating on the bank in the near future (Mendis, 1965). The increased fishing effort with the possibility of still further increase calls for proper management practices by those concerned, in order to obtain the maximum sustained yield from the demersal stock. For this purpose a detailed study of the past performance of the fishery is essential. With this in view all records of commercial operations up to 1960 are being analysed by the present author and are to be published in a series. This is the first paper in the series and gives a detailed analysis of the first commercial trawling operations from 1928 to 1935. Since there had been a major break of about 10 years between this and the present fishery this data is being analysed separately.

A report of the fisheries catch assessment survey (CAS) in the Ugandan waters of Lake Victoria for July 2005

This report presents findings of the first CAS in the Ugandan waters following the agreed SOPs, carried out in July 2005. The findings indicate a total fish catch of 15,047.5 t for July 2005, contributed by Mukene/Dagaa (39.5%), Nile perch (33.1%), Tilapias (17.1%), Haplochromines (9.2%) and other fish species 1.2%. This information gives a new perspective of the estimates of fish production in the Ugandan waters of the lake which are based on field observations. Continuation of support to the CAS programme will certainly get rid of the uncertainties about the fish production levels of the lake which have been there for a long time. This information is vital for fisheries development and fisheries management endeavours.

Population genetic structure of the parasitic nematode Camallanus cotti inferred from DNA sequences of ITS1 rDNA and the mitochondrial COI gene

The population genetic structure of fish parasitic nematode, Camallanus cotti, collected from the Yangtze River, Pearl River and Minjiang River in China was investigated. From these parasites, the similar to 730 bp of the first internal transcribed spacer of ribosomal DNA (ITS1 rDNA) and the 428 bp of mitochondrial cytochrome c oxidase subunit I (COI) gene were sequenced. For the ITS1 rDNA data set, highly significant Fst values and low rates of migration were detected between the Pearl River group and both the Yangtze River (Fst = 0.70, P < 0.00001; Nm = 0.21) and Minjiang River (Fst = 0.73, P < 0.00001; Nm = 0.18) groups, while low Fst value (Fst = 0.018, P > 0.05) and high rate of migration (Nm = 28.42) were found between the Minjiang and the Yangtze rivers. When different host/locality populations (subpopulations) within each river were considered, subpopulations between the Yangtze River and Minjiang River had low Fst values (<= 0.12) and high Nm values (>3.72), while Pearl River subpopulations were significantly different from the Yangtze River and Minjiang River subpopulations (Fst >= 0.59; Nm < 1). The COI gene data set revealed a similar genetic structure. Both phylogenetic analyses and a statistical parsimony network grouped the Pearl River haplotypes into one phylogroup, while the Yangtze River and Minjiang River haplotypes formed a second group. These results suggested that the Yangtze River and Minjiang River subpopulations constituted a single reproductive pool that was distinct from the Pearl River subpopulations. In addition, the present study did not find host-related genetic differentiation occurring in the same drainage. (C) 2009 Published by Elsevier B.V.

Magnetointersubband oscillations of the two-dimensional electron gas in AlxGa1-xN/GaN heterostructures

Shubmkov-de Haas (SdH) measurements are performed over a temperature range of 1.5-20K in AL(0.22)Ga(0.78)N/GaN heterostructures with two subbands occupied. In addition to an intermodulation between two sets of SdH oscillations from the first and second subbands, a beating in oscillatory magnetoresistance at 12K is observed, due to the mixing of the first subband SdH oscillations and 'magnetointersubband' (MIS) oscillations. A phase shift of pi between the SdH and MIS oscillations is also clearly identified. Our experimental results, i.e. that the SdH oscillations dominate at low temperature and MIS oscillations dominate at high temperature, fully comply with the expected behaviour of MIS oscillations.