Die vorliegende Dissertation behandelt zum einen die mechanistischen Details von Bindungsaktivierungs-Reaktionen an Disauerstoff und weißem Phosphor mit den Komplexfragmenten 1[Ni(iPr2Im)2] und 3[(η5-C5H5)Co(iPr2Im)] und zum anderen die Regioselektivität von oxidativen Insertionsreaktionen des 1[Ni(iPr2Im)2]-Komplexfragments in C–X-Bindungen substituierter Fluoraromaten (X = F, OCH3, CN, H). / The presented thesis deals with the mechanistic details of bond activation reactions of the oxygen molecule and white phosphorus at the reactive complex fragments 1[Ni(iPr2Im)2] and 3[(η5-C5H5)Co(iPr2Im)] and with the regioselectivity of oxidative insertion reactions of the 1[Ni(iPr2Im)2]-fragment into C–X-bonds of functionalized fluorinated derivatives of benzene.

<p>The Arbuscular mycorrhiza (AM) is an endosymbiont of higher plant roots. Most land plants and cultivated crops are concerned to AM symbiosis. This endosymbiosis is based on the mutual exchange of nutrients between plant and fungus. Therefore, AM symbiosis leads to an increased demand for photosynthetic products. The aim of this study was to investigate the pathway used by plants during AM symbiosis to increase photosynthetic performance. Therefore, we have carried out a systematic characterization of photosynthesis in Medicago truncatula (M. truncatula), which is a model legume. We observed colonization by the fungus in roots and that AM symbiosis increases the fresh and dry plant biomass. This could be attributed to an increase in both photosynthetic efficiency and capacity in AM plants. Consistent with these observations, AM symbiosis enhanced phosphorus uptake from the soil into roots, stems and leaves, as based on analyses of phosphorus content. Based on equal chl loading, no differences were found regarding D1, Lhcb1 and Lhcb2 protein content in four plant groups. This indicates similar ratio between chl and PSII proteins. Furthermore, AM symbiosis increases the amount of chlorophyll, steady state oxygen evolution activities, maximum quantum yield (Fv/Fm), and photosynthetic electron transport rate (about 5 fold). Nevertheless, photoprotection was not affected by AM symbiosis. We observed an increase in weight of seed/fruit and weight of seed/plant in AM plants (about 2 fold). Based on these results, we propose that AM symbiosis increases both the efficiency and the capacity of photosynthetic apparatus in the M. truncatula.</p>

<p><font face="Arial"> <p align="left">The aim of this study is to compare proximal caries depth on unenhanced storage phosphor plate images and conventional film images. The phosphor plate images were then copied by increasing and decreasing both contrast and brightness respectively. The enhanced phosphor plate images were compared with the unenhanced storage phosphor plate images and conventional film images for the detection of proximal caries diagnosis.</p> </font></p>

Das Ziel der vorliegenden Arbeit war es, die Wachstumsbedingung der nicht kollagenen Knochenproteine auf unterschiedlichen Konversionsoberflächen zu untersuchen. Dazu wurde das Proliferations- sowie Apoptoseverhalten der Knochenproteine in vitro bestimmt. Es kamen neben dem Probekörper Titan als Negativstandard und Ticer als Positivstandard, vier weitere Probekörper auf Titanbasis mit unterschiedlicher Kalzium-Phosphorrelation zur Anwendung. Diese wurden mit humanen Knochenzellen beschickt und über einen Zeitraum vom 3., 5., 7., und 10. Versuchstag ausgewertet. Die Zellkerne und Apoptosefragmente wurden immunhistochemisch markiert und fluoreszenzoptisch untersucht. Desweiteren wurden die relativen Grauwerte ermittelt, welche die Intensität des Bildes wiedergeben. Es zeigte sich in überwiegenden Fällen eine Zunahme der Zellanzahlen auf den verschiedenen Probekörpern. Dagegen verhielt sich die Zahl der apoptotischen Fragmente invers, indem sie auf ein Minimum absanken. In unserer Arbeit kommen wir zu der Annahme, dass Oberflächenmodifikationen die Knochenmineralisierung in der Phase der Knochenneubildung um das Implantat herum, respektive um die Oberflächenstruktur des Implantates, signifikant verbessern. Durch die Beschichtung der Implantatoberflächen mit Kalzium-Phosphor wird einerseits die Oberflächenrauigkeit erhöht, andererseits die Anbindung vom Implantat an die Knochenstruktur verbessert.

Luminescent materials can be found in a broad range of everyday applications. While in the seventies and eighties, the field of luminescent materials seemed to be fairly well covered, research in nineties has been revitalized both in industry and academia. Improvements over the last three decades have led to phosphor materials that operate close to their physical limits. It cannot be expected that properties such as quantum yield and spectral energy distribution will be significantly improved or that distinctly better materials will be found in the near future. Recently, there is a considerable research activity in the field of luminescent materials for lighting and displays to improve the chemical stability and to adopt the materials to the production technology. Ongoing miniaturization, lifetime improvement and spectral stability of fluorescent lamps on the one hand and brightness and contrast improvement in imaging systems on the other hand demand luminescent materials with very high stability that is invariable to operating conditions. All of the today's efficient lighting sources are based on either direct or indirect light emission from plasma discharges. During the pioneering stage, fluorescent lamp industries predominantly used mixtures of two photo luminescent materials: (Zn,Be)2SiO4.'Mn2+ having two emission maxima at 520 and 600 nm and MgW04 with 480 nm emission. The emission from these two phosphors covers the major portion of the visible spectrum. However, the compound (Zn,Be)2Si04 is hazardous to health because of its beryllium content. In 1942, Jenkins showed that Ca5(PO4)3(F,Cl):Sb,Mn was a very efficient emitter. The halophosphates emit both in the blue (Sb3+) as well as in the orange (Mn2+) spectral region, thus in addition yield white light. By carefully adjusting the ratio of Sb3+ and Mn2+ ion concentrations, a white light emitting phosphor was obtained with color temperatures ranging between 6500 and 2700K. However, the drawback of the halophosphate lamps is that it is impossible to have simultaneously high brightness and high color rendering; if the brightness is high (efficacy -80 lm W"1), the color rendering index (CRI) is of the order of 60, the CRI value can be improved up to 90, but then brightness decreases (-50 lm W"1). In 1974, another important breakthrough came in the form of compact fluorescent lamp, based on the trichromatic phosphor blend which resulted color rending values of 80-85 (color 80 lamps) at high efficiencies of 100 lm W"1. The fluorescent lamps with very high color rendering and efficiency can be obtained if three narrow band emitters with emission maxima at 450, 540 and 610 nm are employed. A typical trichromatic lamp phosphor blend comprises of (i) Sr5(PO4)3Cl:Eu2\ BaMgAl1()O,7:Eu2' as blue component, (ii) Ce0.67Tbo.33MgAl,,0,9, LaPO4,Le3\Tb3+ as green component and (iii)Y2C>3:Eiru as the red component. The color 80 lamps employ line emitters that generated light in discrete wavelength intervals. Colored objects that absorb outside these spectral regions appear with a slightly different body color when illuminated with these lamps rather than with a black body radiator such as the light bulb. For these purposes, color 90 or Deluxe lamps have been developed. The emission maximum of the blue phosphor can be shifted towards longer Wavelength by substituting BaMgAli0Oi7:Eu2+ with Sr4Ali4025:Eu2+. The red and green line emitters can be substituted by broad band emitters covering the whole spectral range. For this concept, (Ce,Gd,Tb)MgB5Oi0:Mn has been developed as a red emitter in which energy transfer from Ce3+ via Gd3+ to Mn2+ gives rise to an additional broad band at 630 nm. On the other hand, (Ba,Sr,Ca)2Si04:Eu has been developed as an alternative green-band emitter in which depending on the exact composition, the phosphor emits between 550 and 580 nm with a high quantum yield. Unfortunately, the host lattice is not stable in water, which prevents its deposition on the lamp bulb from aqueous suspensions and for environmental reasons more and more lamps producers use water as the suspending solvent in production instead of butyl acetate. Therefore, it is necessary to develop a new full color emitting phosphors, which has both thermal and chemical stability for application in luminescent lighting. The classical cathode ray tube (CRT) invented as the brown tube more than 100 years ago has developed into a remarkably mature product considering the complexity of its manufacturing process. Cathode rays are a beam of fast electrons, the accelerating voltage in a television picture tube is high (>10 kV). Basic requirements of display phosphors are stability (2000 hr operation) and emission color purity according to the standards set by the European Broadcasting Union (EBU). The blue and green phosphors are still the very cheep ZnS based materials, essentially the same ever since color-TV was introduced in fifties. On the other hand, (Zn,Cd)S, Ag+,C1" was originally used as the red phosphor however, the broad emission centered at 650 nm due to intrinsic donor-acceptor transition leads to rather low lumen equivalent as large fraction of the emission integral lies outside the eye sensitivity curve. For this and the environmental reasons, it has been replaced by the much more expensive Y2O2S:Eu with main emission lines at 612 and 628 nm. Recently, the big electronic companies are trying to enforce flat panel displays e.g. PDPs (plasma display panels) and FEDs (field emission displays). This is because of the fact that when compared to the CRT screen pigments, FED phosphors are required to operate at lower voltages and higher current densities. Although the voltages used in FEDs are only 0.1 to < 2 kV, the high-energy surface excitation on the phosphor particles causes degradation of sulfides, leaving the oxide hosts as the only favorable choice. The phosphor blends used are mixtures of SrTiO3:Pr3+ (red), Y2Si05:Tb (green) and Y2Si05:Ce (blue). However, the white light generation efficiency is very low (-5 lm W"1) and required improvement of phosphor efficacy because of its distinct advantages such as a very wide range of operational temperatures, stability under rugged conditions and wide viewing angle of emission. Similarly, in PDPs blue emitting BaMgAlioOniEu, green emitting Z^SiO^Mn and red emitting (Y,Gd)BO3:Eu are mostly used which shows a screen efficiency of about 1.5 lm W"1, just only half that of a CRT used in today's TV sets. However, the advantages of PDPs over CRTs are that it is not sensitive towards the display manufacturing process, which includes high temperature annealing up to about 600°C and it is stable under the harsh conditions of a Ne/Xe plasma used in PDPs (ion bombardment, VUV radiation). This puts pressure on the development of phosphor for maximum brightness and high stability to replace completely the classical CRTs. On the other hand, the invention of the blue-light emitting diode (LED) based on GaN can be regarded as a triumph of materials chemistry. In principle, it is possible to vary the emission wavelength of blue GaN-based LEDs between 370 nm (band-gap of pure GaN) and 470 nm by increasing the indium (In) content in InGaN devices. Assuming a conversion from the incident light by a phosphor material emitting at 555 nm, InGaN is coated with (Yi.xGdx)3(Ali-yGay)5Oi2:Ce (YAG:Ce) which has broad yellow band varying between 510 and 580 nm. This allows the adjustment of white color temperature from 8000 down to 3000 K. Recently, S^SiCU and S^SiOs have attracted current interest due to their potential applications in developing white light-emitting-diodes (LEDs) because GaN (400 nm chip)-coated with Sr2Si04:Eu2+ or Sr3SiC>5;Eu2+ exhibits better luminous efficiency than that of the industrially available product such as InGaN (460 nm chip)-coated with YAG:Ce. However, the major drawback of this combination is the strongly decreasing overall efficiency upon lowering the color temperature. This can be solved by using a phosphor material that has sufficient absorption at the emission wavelength of the blue diode, the quantum yield should be high under UV/Vis excitation and the FWHM of the emission band should be as small as possible in order to achieve high luminous output. The search for stable inorganic rare-earths phosphors with high absoiption in the near UV/blue spectral region is therefore an attractive research work. Since luminescence materials are a key component for lighting and display concept, research in the field of rare-earths doped oxide phosphors is carried out. Although state-of-the-art materials fulfill most requirements, improvements are still necessary to further boost the efficiency of the phosphor materials. Since it is not expected that materials will be found that perform better than the already established phosphor, the present work concentrates on the improvements of the phosphor by modifying the chemical and niicrostructurai features as well as the crystal structure. Chapter I gives a brief introduction to luminescence in solids, physical aspects and applications. Chapter II describes the synthesis and various experimental techniques employed in the investigation. Chapter III deals with photoluminescence and energy transfer involving charge transfer states in Sr2-xLnxCe04+x/2 (Ln = Eu and Sm) leading to an efficient full color emitting phosphor for luminescent lighting. Chapter IV and V describe charge transfer transition involving interface states associated with transitional nanophaseprecipitates leading to photoluminescence enhancement of SrTiO3:Pr3+,Al3+ and SrAli2Oi9:Pr3+,Ti4\ The light induced charge transfer leading to changing oxidation state of Eu in Sr2Si04 involving transient crystal structure results an efficient material for optical storage is presented in Chapter VI.Photoluminescence due to efficient energy transfer from Ce3+ to Tb3+ and Mn2t in SnAlioSi02o leading to an efficient phosphor for FEDs is presented in Chapter VII. Chapter VIII describes charge transfer transition involving trap states leading to long phosphorescence in SrAl2-xBxO4 (0<x<0.2) and Sr4Al14.xBxO25 (0.1<x<0.4) co-doped with Eu2+ and Dy3+. Chapter IX presents the role of particle size on the charge transfer associated luminescence of GdVO4:Ln3+ (Ln = Eu and Sm). A summary of the important findings and the conclusions arrived on the basis of results from these investigations are presented at the end of the thesis.

<p><font face="Arial"> <p align="left">The aim of this study is to compare proximal caries depth on unenhanced storage phosphor plate images and conventional film images. The phosphor plate images were then copied by increasing and decreasing both contrast and brightness respectively. The enhanced phosphor plate images were compared with the unenhanced storage phosphor plate images and conventional film images for the detection of proximal caries diagnosis.</p> </font></p>

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-04-04T18:47:22Z No. of bitstreams: 1 Diserta__o_1__1_[1].Anderson.2006.pdf: 1438542 bytes, checksum: 234cce5096f0e435dca87119bb754345 (MD5) / Made available in DSpace on 2017-04-04T18:47:22Z (GMT). No. of bitstreams: 1 Diserta__o_1__1_[1].Anderson.2006.pdf: 1438542 bytes, checksum: 234cce5096f0e435dca87119bb754345 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica Ambiental. Niterói, RJ / O sedimento e a vegetação de manguezal podem influenciar a qualidade ambiental de áreas afetadas por efluentes urbanos devido à retenção ou incorporação de contaminantes como o fósforo. Considerando a importância dos manguezais, e a dinâmica do fósforo para este ecossistema, este trabalho caracterizou as formas de fósforo em sedimentos de manguezal de Mauá (Baía de Guanabara), usando o fracionamento do fósforo entre formas orgânicas e inorgânicas. Para a realização deste trabalho foram feitas coletas de sete testemunhos de sedimento, localizados: (1) na planície de lama onde não havia presença de manguezal (testemunho PL); (2) em áreas com a vegetação de manguezal degradada provavelmente por cortes (testemunhos MD1 e MD2); (3) onde a vegetação foi morta provavelmente por pragas (testemunho MP); (4) onde o manguezal tem árvores senescentes (testemunho MS); (5) onde a vegetação estava aparentemente saudável (testemunhos MV1 e MV2). Os resultados mostraram que os valores médios do fósforo inorgânico (PI) no sedimento diminuem em direção ao continente. Esta variação pode ser explicada pela incorporação do PI pela vegetação de manguezal que também está preservada neste sentido. Os testemunhos MD1 e MD2 apresentam os valores de PI mais elevados da área. Esse resultado pode ser explicado por estes pontos apresentarem sedimentos de cor marrom, evidenciando serem sedimentos oxidados e estes têm uma forte tendência de seqüestrar o PI. O aumento do PI nos testemunhos PL, MD1, MD2, MP, e MS em direção à superfície dos testemunhos, provavelmente se deve ao aumento do aporte de efluentes urbanos a partir de 1950 (dados de 210Pb), que coincide com o aumento da população urbana do Rio de Janeiro. Os valores médios de fósforo orgânico (PO) e matéria orgânica (MO) aumentam em direção ao continente. Esses dados podem ser explicados pela preservação da floresta nos testemunhos mais próximos do continente. O percentual %PO no testemunho PL é 16% e este testemunho tem forte correlação negativa da MO com o PO. Os testemunhos MD1 e MD2 apresentam %PO igual a 6% e 17%, respectivamente. Estes testemunhos apresentam fraca correlação da MO com o PO. No testemunho MP o %PO é igual a 55% e este testemunho tem fraca correlação da MO com o PO. Estes resultados evidenciam que a MO e o PO têm diferentes origens. No testemunho MS o %PO é 70% e o PO tem forte correlação positiva com a MO. Nos testemunhos MV1 e MV2 o %PO é respectivamente de 90 e 86%. Nestes testemunhos o PO apresenta forte correlação positiva com a MO. A comparação com outros trabalhos na Baía de Guanabara mostrou que o testemunho PL apresenta concentrações de PT próximas das encontradas dentro da área da baía, evidenciando um quadro de contaminação por fósforo neste ambiente. Os resultados evidenciam a importância da vegetação de manguezal para a distribuição e o fracionamento geoquímico do fósforo nos sedimentos estudados. / Sediment and vegetation of mangrove forest can influence the environmental quality of areas affected by urban sewage due to retention or incorporation of contaminants such as phosphorus. Considering the importance of the mangroves and dynamics of the phosphorus for this ecosystem, this work characterizes the organic and the inorganic fractions of phosphorus in sediments of the Mauá mangrove forest (Guanabara Bay). For this study, seven sediment core were collected (1) in the mud flat without presence of mangrove trees (core PL), (2) in areas with vegetation degraded probably by deforestation (cores MD1 and MD2), (3) in areas with dead vegetation probably by insect attacks (core MP), (4) where the mangrove forest has senescent trees (core MS), (5) in an area with vegetation is apparently healthy (core MV1 and MV2). The results showed that the average values of inorganic phosphorus (IP) in the sediment decrease in the continent direction. This variation can be explained by the incorporation of IP by mangrove vegetation also preserved in this direction. Core MD1 and MD2 showed higher values of IP. This result may be explained by a presence of oxidized sediments (with brown color), since oxidized sediments tend to sequester phosphorus. The increase of IP in cores PL, MD1, MD2, MP and MS from bottom to surface problably is due to an increase of urban effluent input since 1950 (210Pb data), in agreement with the increase of the Rio de Janeiro urban population. The average values of organic phosphorus (OP) and organic matter (OM) in the sediment increases in the continental direction. These results can be explained by the preservation of the forest in the cores next to the continent. The %PO in core PL is 16% and this core showed a strong negative correlation of OM with OP. Cores MD1 and MD2 presented a %OP of 6% and 17%, respectively. These cores presented weak correlation of OM with OP. In core MP the %OP is equal to 55% and this core showed weak correlation of OM with OP. These results show that OM and OP have different origins. In core MS, the %OP is 70% and the OP has strong positive correlation with the OM. Cores MV1 and MV2 have %OP of 90 and 86%, respectively. In these cores the OP showed strong positive correlation with OM. The comparison with other studies in Guanabara Bay showed that TP concentrations of core PL closer to those within the bay area, evidencing a context of phosphorus contamination in this environment. The results evidence the importance of mangrove vegetation on phosphorus distribution and geochemical fractionation in sediments.

During the winters in recent years Laholmsbuktens VA's treatment plant in Halmstad has recorded unexcepted levels of phosphorus from the polishing pond. Only between 8 and 20 January 2016 samples indicates a realese of net 75 kg. In winter the pond temperature never goes below about 8oC, which attracts wintering waterfowl. In February 19, 2016 the largest number of birds in the inventory for this thesis was noted, 325 individuals, of which 208 were tufted ducks.  Even if the number of waterfowl at peak levels was to be about 1000 individuals, their combined contribution of phosphorus through droppings into the pond could not be more than 500 g per day. This study proposes that a significant factor is the foraging activity of tufted ducks, which are diving ducks. In search of food at daytime they disturb the sediment at the bottom of the pond, i.e bioturbation.  The higher proportion of particle-bound phosphorus in samples with high phosphorus content also fits well with this hypothesis. A scientific investigation in which the bottom of this part of the pond was stirred up mechanically gave similar proportions between phosphorus and water-soluble phosphorus.

No description available.

Tri(pyrazolyl)phosphane (5R1,R2) werden als alternative, kostengünstige und geringer toxische Phosphorpräkursoren in der Synthese von InP/ZnS Quantenpunkten (QP) eingesetzt. Ausgehend von diesen Vorläuferverbindungen konnten langzeitstabile (>6 Monate) P(OLA)3 (OLAH = Oleylamin) Stammlösungen synthetisiert werden, aus denen sich die entsprechenden Pyrazole einfach zurückgewinnen lassen. P(OLA)3 fungiert in der Synthese von hochemittierenden InP/ZnS QP sowohl als Phosphorquelle als auch als Reduktionsmittel. Die erhaltenen Kern/Schale-Partikel zeichnen sich durch hohe Photolumineszenz-Quantenausbeuten (PL-QA) von 51–62% in einem spektralen Bereich von 530–620 nm aus. Die Verarbeitung und Anwendung dieser InP/ZnS QP als Farbkonversionsschicht wurde als „proof-of-concept“ in einer weißen Leuchtdiode (LED) demonstriert