Calculations on the end-group conformational barrier in carotenoids and a study of the bioavailability of xanthophyll esters in humans

The present study measures the increase in serum carotenoid concentration in 30 healthy individuals after supplementation with a low dose xanthophyll ester (3 and 6 mg of lutein equivalent/per day) when compared to a placebo. Serum levels of carotenoids were measured using HPLC and showed an increase in the concentration of lutein, zeaxanthin and four lutein metabolites proportional to dose. In order to further assess the importance of the end-group structure in carotenoids we have investigated the influence of the end-group type and functionality on the conformational energy barrier. We used the density functional method implemented on GAUSSIAN 98 to calculate the conformational energy curves for rotation of the P-ring or the E-ring relative to short polyene chains around the C6-C7 single bond. A large barrier is observed for the interconversion of conformers in the E-rings (8 kcal/mol) when compared to beta rings (2.3-3 kcal/mol).

Improving performance of a permeable reactive barrier in the degradation of trichloroethylene using ultrasound

The impact of ultrasound on improving the performance of a granular iron Permeable Reactive Barrier (PRB) in the degradation of Trichloroethylene (TCE) was evaluated. Two treatment columns made of clear Plexiglas with a height of 1ft and a diameter of 2 inches and filled with granular iron were used. One was fitted with 25Khz ultrasound probes. A solution of TCE was run through at constant flow rate. Samples obtained from the column at different residence times before and after sonication were analyzed for concentrations of TCE and used to generate concentration profiles to obtain rate constants, which were compared. An improvement of 23.4% in the reaction rate of TCE degradation was observed after sonication of the iron media suggesting that ultrasound may contribute to improving the performance of PRBs in the degradation of TCE in contaminated groundwater.

Modificação do eletrodo AWS E7018 com adição de filmes finos externos de PVC e Al, para soldagem de aço C-Mn

This paper suggests modifications in coating of electrodes providing an alternative for execution of welding with low hydrogen electrode AWS E7018 without having to dry it, reducing thus the cost and time of manufacturing of high resistance welds. The welds in this research were developed with basic coated electrodes (hygroscopic) – SMAW process – externally painted with aluminum spray paint for high temperatures or wrapped with thin plastic films (PVC) and aluminum foil films used commonly for food protection. The basic premise is that establishing a barrier between the atmosphere and the electrode coating could reduce the effects of high hygroscopicity presented by coatings of low hydrogen, minimizing this way the main source of supply of hydrogen to the fusion pool during welding. It is also expected that the addition of new materials from the electrode coating to the fusion pool would induce metallurgical changes in the deposited metal and, as a consequence, modifications in its mechanical properties. This research dealt with measuring the dissolved hydrogen in the deposited metal after welding with modified electrodes, evaluating the influence of these changes in the produced microstructures and in the mechanical properties of the resulting weld, and comparing the obtained results with the standard welding procedures and with the recently developed waterproof electrodes. The results obtained in most samples welded with modified electrodes showed increased mechanical resistance and increased tenacity due to the increased percentage of acicular ferrite in metal deposited without significant elevation of hardness, when compared with the traditional welding with AWS E7018 electrode and with ELBRÁS BRH4R waterproof electrode. The diffusing hydrogen measured in the modified electrodes was kept inside the parameters defined by international codes.

Modificação do eletrodo AWS E7018 com adição de filmes finos externos de PVC e Al, para soldagem de aço C-Mn

This paper suggests modifications in coating of electrodes providing an alternative for execution of welding with low hydrogen electrode AWS E7018 without having to dry it, reducing thus the cost and time of manufacturing of high resistance welds. The welds in this research were developed with basic coated electrodes (hygroscopic) – SMAW process – externally painted with aluminum spray paint for high temperatures or wrapped with thin plastic films (PVC) and aluminum foil films used commonly for food protection. The basic premise is that establishing a barrier between the atmosphere and the electrode coating could reduce the effects of high hygroscopicity presented by coatings of low hydrogen, minimizing this way the main source of supply of hydrogen to the fusion pool during welding. It is also expected that the addition of new materials from the electrode coating to the fusion pool would induce metallurgical changes in the deposited metal and, as a consequence, modifications in its mechanical properties. This research dealt with measuring the dissolved hydrogen in the deposited metal after welding with modified electrodes, evaluating the influence of these changes in the produced microstructures and in the mechanical properties of the resulting weld, and comparing the obtained results with the standard welding procedures and with the recently developed waterproof electrodes. The results obtained in most samples welded with modified electrodes showed increased mechanical resistance and increased tenacity due to the increased percentage of acicular ferrite in metal deposited without significant elevation of hardness, when compared with the traditional welding with AWS E7018 electrode and with ELBRÁS BRH4R waterproof electrode. The diffusing hydrogen measured in the modified electrodes was kept inside the parameters defined by international codes.

Benthic and substrate cover data derived from photo-transect surveys in Lizard Island, Great Barrier Reef conducted on October 3-7, 2012

Underwater georeferenced photo-transect surveys were conducted on October 3-7, 2012 at various sections of the reef and lagoon at Lizard Island, Great Barrier Reef. For this survey a snorkeler swam while taking photos of the benthos at a set distance from the benthos using a standard digital camera and towing a GPS in a surface float which logged the track every five seconds. A Canon G12 digital camera was placed in a Canon underwater housing and photos were taken at 1 m height above the benthos. Horizontal distance between photos was estimated by three fin kicks of the survey snorkeler, which corresponded to a surface distance of approximately 2.0 - 4.0 m. The GPS was placed in a dry bag and logged the position at the surface while being towed by the photographer (Roelfsema, 2009). A total of 1,265 benthic photos were taken. Approximation of coordinates of each benthic photo was conducted based on the photo timestamp and GPS coordinate time stamp, using GPS Photo Link Software (www.geospatialexperts.com). Coordinates of each photo were interpolated by finding the GPS coordinates that were logged at a set time before and after the photo was captured. Benthic or substrate cover data was derived from each photo by randomly placing 24 points over each image using the Coral Point Count for Microsoft Excel program (Kohler and Gill, 2006). Each point was then assigned to 1 of 79 cover types, which represented the benthic feature beneath it. Benthic cover composition summary of each photo scores was generated automatically using CPCE program. The resulting benthic cover data of each photo was linked to GPS coordinates, saved as an ArcMap point shapefile, and projected to Universal Transverse Mercator WGS84 Zone 55 South.

Geochemical parameters of sediments and waters in areas of ocean barrier zones

Geochemical barrier zones play an important role in determining various physical systems and characteristics of oceans, e.g. hydrodynamics, salinity, temperature and light. In the book each of more than 30 barrier zones are illustrated and defined by physical, chemical and biological parameters. Among the topics discussed are processes of inflow, transformation and precipitation of the sedimentary layer of the open oceans and more restricted areas such as the Baltic, Black and Mediterranean Seas.

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy.

Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD’s thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2’s bandgap, can have a strong dependence on TiO2’s thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency.

In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

Results of wave modelling for Moreton Bay, Southeast Queensland, and a reef lagoon off Lizard Island, Great Barrier Reef, Australia

The distribution, abundance, behaviour, and morphology of marine species is affected by spatial variability in the wave environment. Maps of wave metrics (e.g. significant wave height Hs, peak energy wave period Tp, and benthic wave orbital velocity URMS) are therefore useful for predictive ecological models of marine species and ecosystems. A number of techniques are available to generate maps of wave metrics, with varying levels of complexity in terms of input data requirements, operator knowledge, and computation time. Relatively simple "fetch-based" models are generated using geographic information system (GIS) layers of bathymetry and dominant wind speed and direction. More complex, but computationally expensive, "process-based" models are generated using numerical models such as the Simulating Waves Nearshore (SWAN) model. We generated maps of wave metrics based on both fetch-based and process-based models and asked whether predictive performance in models of benthic marine habitats differed. Predictive models of seagrass distribution for Moreton Bay, Southeast Queensland, and Lizard Island, Great Barrier Reef, Australia, were generated using maps based on each type of wave model. For Lizard Island, performance of the process-based wave maps was significantly better for describing the presence of seagrass, based on Hs, Tp, and URMS. Conversely, for the predictive model of seagrass in Moreton Bay, based on benthic light availability and Hs, there was no difference in performance using the maps of the different wave metrics. For predictive models where wave metrics are the dominant factor determining ecological processes it is recommended that process-based models be used. Our results suggest that for models where wave metrics provide secondarily useful information, either fetch- or process-based models may be equally useful.

Seawater carbonate chemistry and calcification during tropical reef studies at Younge reef (Great Barrier Reef), 1996

Community metabolism was investigated using a Lagrangian flow respirometry technique on 2 reef flats at Moorea (French Polynesia) during austral winter and Yonge Reef (Great Barrier Reef) during austral summer. The data were used to estimate related air-sea CO2 disequilibrium. A sine function did not satisfactorily model the diel light curves and overestimated the metabolic parameters. The ranges of community gross primary production and respiration (Pg and R; 9 to 15 g C m-2 d-1) were within the range previously reported for reef flats, and community net calcification (G; 19 to 25 g CaCO3 m-2 d-1) was higher than the 'standard' range. The molar ratio of organic to inorganic carbon uptake was 6:1 for both sites. The reef flat at Moorea displayed a higher rate of organic production and a lower rate of calcification compared to previous measurements carried out during austral summer. The approximate uncertainty of the daily metabolic parameters was estimated using a procedure based on a Monte Carlo simulation. The standard errors of Pg,R and Pg/R expressed as a percentage of the mean are lower than 3% but are comparatively larger for E, the excess production (6 to 78%). The daily air-sea CO2 flux (FCO2) was positive throughout the field experiments, indicating that the reef flats at Moorea and Yonge Reef released CO2 to the atmosphere at the time of measurement. FCO2 decreased as a function of increasing daily irradiance.

TILTED COLUMNAR THIN FILM COATINGS WITH ANISOTROPIC LIGHT SCATTERING PROPERTIES FOR SOLAR ENERGY APPLICATIONS

The main goal of this thesis is to show the versatility of glancing angle deposition (GLAD) thin films in applications. This research is first focused on studying the effect of select deposition variables in GLAD thin films and secondly, to demonstrate the flexibility of GLAD films to be incorporated in two different applications: (1) as a reflective coating in low-level concentration photovoltaic systems, and (2) as an anode structure in dye-sensitized solar cells (DSSC). A particular type of microstructure composed of tilted micro-columns of titanium is fabricated by GLAD. The microstructures form elongated and fan-like tilted micro-columns that demonstrate anisotropic scattering. The thin films texture changes from fiber texture to tilted fiber texture by increasing the vapor incidence angle. At very large deposition angles, biaxial texture forms. The morphology of the thin films deposited under extreme shadowing condition and at high temperature (below recrystallization zone) shows a porous and inclined micro-columnar morphology, resulting from the dominance of shadowing over adatom surface diffusion. The anisotropic scattering behavior of the tilted Ti thin film coatings is quantified by bidirectional reflectance distribution function (BRDF) measurements and is found to be consistent with reflectance from the microstructure acting as an array of inclined micro-mirrors that redirect the incident light in a non-specular reflection. A silver-coating of the surface of the tilted-Ti micro-columns is performed to enhance the total reflectance of the Ti-thin films while keeping the anisotropic scattering behavior. By using such coating is as a booster reflector in a laboratory-scale low-level concentration photovoltaic system, the short-circuit current of the reference silicon solar cell by 25%. Finally, based on the scattering properties of the tilted microcolumnar microstructure, its scattering effect is studied as a part of titanium dioxide microstructure for the anode in DSSCs. GLAD-fabricated TiO2 microstructures for the anode in a DSSC, consisting of vertical micro-columns, and combined vertical topped with tilted micro-columns are compared. The solar cell with the two-part microstructure shows the highest monochromatic incident photon to current efficiency with 20% improvement compared to the vertical microstructure, and the efficiency of the cell increases from 1.5% to 2% due to employing the scattering layer.

The restorative role of annexin A1 at the blood–brain barrier

Annexin A1 is a potent anti-inflammatory molecule that has been extensively studied in the peripheral immune system, but has not as yet been exploited as a therapeutic target/agent. In the last decade, we have undertaken the study of this molecule in the central nervous system (CNS), focusing particularly on the primary interface between the peripheral body and CNS: the blood–brain barrier. In this review, we provide an overview of the role of this molecule in the brain, with a particular emphasis on its functions in the endothelium of the blood–brain barrier, and the protective actions the molecule may exert in neuroinflammatory, neurovascular and metabolic disease. We focus on the possible new therapeutic avenues opened up by an increased understanding of the role of annexin A1 in the CNS vasculature, and its potential for repairing blood–brain barrier damage in disease and aging.