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The development of fast and reliable biochemical tools for on-site screening in environmental analysis was the main target of the present work. Due to various hazardous effects such as endocrine disruption and toxicity phenolic compounds are key analytes in environmental analysis and thus were chosen as model analytes. Three different methods were developed: For the enzymatic detection of phenols in environmental samples an enzyme-based biosensor was developed. In contrast to reported work using tyrosinase or peroxidases, we developed a biosensor based on glucose dehydrogenase as biorecognition element. This biosensor was devoted for an application in a laboratory flow system as well as in a portable device for on-site measurements. This enzymatic detection is applicable only for a limited number of phenols due to substrate specificity of the enzyme. For other relevant compounds based on a phenolic structure (i.e. nitrophenol, alkylphenols and alkylphenol ethoxylates) immunological methods had to be developed. The electrochemical GDH-biosensor was used as the label detector in these immunoassays. Two heterogeneous immunoassays were developed where ßGal was used as the label. An electrochemical method for the determination of the marker enzyme activity was processed. The separation step was realized with protein A/G columns (laboratory flow system) or by direct immobilization of the antibodies in small disposable capillaries (on-site analysis). All methods were targeted on the contemporary analysis of small numbers of samples.
Late Miocene to Quaternary volcanic rocks from the frontal arc to the back-arc region of the Central Volcanic Zone in the Andes show a wide range of delta 11B values (+4 to -7 ‰) and boron concentrations (6 to 60 ppm). Positive delta 11B values of samples from the volcanic front indicate involvement of a 11B-enriched slab component, most likely derived from altered oceanic crust, despite the thick Andean continental lithosphere, and rule out a pure crust-mantle origin for these lavas. The delta 11B values and B concentrations in the lavas decrease systematically with increasing depth of the Wadati-Benioff Zone. This across-arc variation in delta 11B values and decreasing B/Nb ratios from the arc to the back-arc samples are attributed to the combined effects of B-isotope fractionation during progressive dehydration in the slab and a steady decrease in slab-fluid flux towards the back arc, coupled with a relatively constant degree of crustal contamination as indicated by similar Sr, Nd and Pb isotope ratios in all samples. Modelling of fluid-mineral B-isotope fractionation as a function of temperature fits the across-arc variation in delta 11B and we conclude that the B-isotope composition of arc volcanics is dominated by changing delta 11B composition of B-rich slab-fluids during progressive dehydration. Crustal contamination becomes more important towards the back-arc due to the decrease in slab-derived fluid flux. Because of this isotope fractionation effect, high delta 11B signatures in volcanic arcs need not necessarily reflect differences in the initial composition of the subducting slab. Three-component mixing calculations for slab-derived fluid, the mantle wedge and the continental crust based on B, Sr and Nd isotope data indicate that the slab-fluid component dominates the B composition of the fertile mantle and that the primary arc magmas were contaminated by an average addition of 15 to 30 % crustal material.
In this thesis the gravitational lensing effect is used to explore a number of cosmological topics. We determine the time delay in the gravitationally lensed quasar system HE1104-1805 using different techniques. We obtain a time delay Delta_t(A-B) Delta_t(A-B) =-310 +- 20 days (2 sigma errors) between the two components. We also study the double quasar Q0957+561 during a three years monitoring campaign. The fluctuations we find in the difference light curves are completely consistent with noise and no microlensing is needed to explain these fluctuations. Microlensing is also studied in the quadruple quasar Q2237+0305 during the GLITP collaboration (Oct.1999-Feb.2000). We use the absence of a strong microlensing signal to obtain an upper limit of v=600 km/s for the effective transverse velocity of the lens galaxy (considering microlenses with 0.1 solar masses). The distribution of dark matter in galaxy clusters is also studied in the second part of the thesis. In the cluster of galaxies Cl0024+1654 we obtain a mass-to-light ratio of M/L = 200 M_sun/L_sun (within a radius of 3 arcminutes). In the galaxy cluster RBS380 we find a relatively low X-ray luminosity for a massive cluster of L =2*10^(44) erg/s, but a rich distribution of galaxies in the optical band.
The colloidal systems are present everywhere in many varieties such as emulsions (liquid droplets dispersed in liquid), aerosols (liquid dispersed in gas), foam (gas in liquid), etc. Among several new methods for the preparation of colloids, the so-called miniemulsion technique has been shown to be one of the most promising. Miniemulsions are defined as stable emulsions consisting of droplets with a size of 50-500 nm by shearing a system containing oil, water, a surfactant, and a highly water insoluble compound, the so-called hydrophobe 1. In the first part of this work, dynamic crystallization and melting experiments are described which were performed in small, stable and narrowly distributed nanodroplets (confined systems) of miniemulsions. Both regular and inverse systems were examined, characterizing, first, the crystallization of hexadecane, secondly, the crystallization of ice. It was shown for both cases that the temperature of crystallization in such droplets is significantly decreased (or the required undercooling is increased) as compared to the bulk material. This was attributed to a very effective suppression of heterogeneous nucleation. It was also found that the required undercooling depends on the nanodroplet size: with decreasing droplet size the undercooling increases. 2. It is shown that the temperature of crystallization of other n-alkanes in nanodroplets is also significantly decreased as compared to the bulk material due to a very effective suppression of heterogeneous nucleation. A very different behavior was detected between odd and even alkanes. In even alkanes, the confinement in small droplets changes the crystal structure from a triclinic (as seen in bulk) to an orthorhombic structure, which is attributed to finite size effects inside the droplets. An intermediate metastable rotator phase is of less relevance for the miniemulsion droplets than in the bulk. For odd alkanes, only a strong temperature shift compared to the bulk system is observed, but no structure change. A triclinic structure is formed both in bulk and in miniemulsion droplets. 3. In the next part of the thesis it is shown how miniemulsions could be successfully applied in the development of materials with potential application in pharmaceutical and medical fields. The production of cross-linked gelatin nanoparticles is feasible. Starting from an inverse miniemulsion, the softness of the particles can be controlled by varying the initial concentration, amount of cross-link agent, time of cross-linking, among other parameters. Such particles show a thermo-reversible effect, e.g. the particles swell in water above 37 °C and shrink below this temperature. Above 37 °C the chains loose the physical cross-linking, however the particles do not loose their integrity, because of the chemical cross-linking. Those particles have potential use as drug carriers, since gelatin is a natural polymer derived from collagen. 4. The cross-linked gelatin nanoparticles have been used for the biomineralization of hydroxyapatite (HAP), a biomineral, which is the major constituent of our bones. The biomineralization of HAP crystals within the gelatin nanoparticles results in a hybrid material, which has potential use as a bone repair material. 5. In the last part of this work we have shown that layers of conjugated semiconducting polymers can be deposited from aqueous dispersion prepared by the miniemulsion process. Dispersions of particles of different conjugated semiconducting polymers such as a ladder-type poly(para-phenylene) and several soluble derivatives of polyfluorene could be prepared with well-controlled particle sizes ranging between 70 - 250 nm. Layers of polymer blends were prepared with controlled lateral dimensions of phase separation on sub-micrometer scales, utilizing either a mixture of single component nanoparticles or nanoparticles containing two polymers. From the results of energy transfer it is demonstrated that blending two polymers in the same particle leads to a higher efficiency due to the better contact between the polymers. Such an effect is of great interest for the fabrication of opto-electronic devices such as light emitting diodes with nanometer size emitting points and solar cells comprising of blends of electron donating and electron accepting polymers.
Encounters with neighbours
(2003)
In this work, different aspects and applications of the recurrence plot analysis are presented. First, a comprehensive overview of recurrence plots and their quantification possibilities is given. New measures of complexity are defined by using geometrical structures of recurrence plots. These measures are capable to find chaos-chaos transitions in processes. Furthermore, a bivariate extension to cross recurrence plots is studied. Cross recurrence plots exhibit characteristic structures which can be used for the study of differences between two processes or for the alignment and search for matching sequences of two data series. The selected applications of the introduced techniques to various kind of data demonstrate their ability. Analysis of recurrence plots can be adopted to the specific problem and thus opens a wide field of potential applications. Regarding the quantification of recurrence plots, chaos-chaos transitions can be found in heart rate variability data before the onset of life threatening cardiac arrhythmias. This may be of importance for the therapy of such cardiac arrhythmias. The quantification of recurrence plots allows to study transitions in brain during cognitive experiments on the base of single trials. Traditionally, for the finding of these transitions the averaging of a collection of single trials is needed. Using cross recurrence plots, the existence of an El Niño/Southern Oscillation-like oscillation is traced in northwestern Argentina 34,000 yrs. ago. In further applications to geological data, cross recurrence plots are used for time scale alignment of different borehole data and for dating a geological profile with a reference data set. Additional examples from molecular biology and speech recognition emphasize the suitability of cross recurrence plots.