Use of computer algebra in the calculation of Feynman diagrams

The increasing precision of current and future experiments in high-energy physics requires a likewise increase in the accuracy of the calculation of theoretical predictions, in order to find evidence for possible deviations of the generally accepted Standard Model of elementary particles and interactions. Calculating the experimentally measurable cross sections of scattering and decay processes to a higher accuracy directly translates into including higher order radiative corrections in the calculation. The large number of particles and interactions in the full Standard Model results in an exponentially growing number of Feynman diagrams contributing to any given process in higher orders. Additionally, the appearance of multiple independent mass scales makes even the calculation of single diagrams non-trivial. For over two decades now, the only way to cope with these issues has been to rely on the assistance of computers. The aim of the xloops project is to provide the necessary tools to automate the calculation procedures as far as possible, including the generation of the contributing diagrams and the evaluation of the resulting Feynman integrals. The latter is based on the techniques developed in Mainz for solving one- and two-loop diagrams in a general and systematic way using parallel/orthogonal space methods. These techniques involve a considerable amount of symbolic computations. During the development of xloops it was found that conventional computer algebra systems were not a suitable implementation environment. For this reason, a new system called GiNaC has been created, which allows the development of large-scale symbolic applications in an object-oriented fashion within the C++ programming language. This system, which is now also in use for other projects besides xloops, is the main focus of this thesis. The implementation of GiNaC as a C++ library sets it apart from other algebraic systems. Our results prove that a highly efficient symbolic manipulator can be designed in an object-oriented way, and that having a very fine granularity of objects is also feasible. The xloops-related parts of this work consist of a new implementation, based on GiNaC, of functions for calculating one-loop Feynman integrals that already existed in the original xloops program, as well as the addition of supplementary modules belonging to the interface between the library of integral functions and the diagram generator.

Advances in understanding of osmotic dehydration and vacuum impregnation of fruits

Osmotic Dehydration and Vacuum Impregnation are interesting operations in the food industry with applications in minimal fruit processing and/or freezing, allowing to develop new products with specific innovative characteristics. Osmotic dehydration is widely used for the partial removal of water from cellular tissue by immersion in hypertonic (osmotic) solution. The driving force for the diffusion of water from the tissue is provided by the differences in water chemical potential between the external solution and the internal liquid phase of the cells. Vacuum Impregnation of porous products immersed in a liquid phase consist of reduction of pressure in a solid-liquid system (vacuum step) followed by the restoration of atmospheric pressure (atmospheric step). During the vacuum step the internal gas in the product pores is expanded and partially flows out while during the atmospheric step, there is a compression of residual gas and the external liquid flows into the pores (Fito, 1994). This process is also a very useful unit operation in food engineering as it allows to introduce specific solutes in the tissue which can play different functions (antioxidants, pH regulators, preservatives, cryoprotectants etc.). The present study attempts to enhance our understanding and knowledge of fruit as living organism, interacting dynamically with the environment, and to explore metabolic, structural, physico-chemical changes during fruit processing. The use of innovative approaches and/or technologies such as SAFES (Systematic Approach to Food Engineering System), LF-NMR (Low Frequency Nuclear Magnetic Resonance), GASMAS (Gas in Scattering Media Absorption Spectroscopy) are very promising to deeply study these phenomena. SAFES methodology was applied in order to study irreversibility of the structural changes of kiwifruit during short time of osmotic treatment. The results showed that the deformed tissue can recover its initial state 300 min after osmotic dehydration at 25 °C. The LF-NMR resulted very useful in water status and compartmentalization study, permitting to separate observation of three different water population presented in vacuole, cytoplasm plus extracellular space and cell wall. GASMAS techniques was able to study the pressure equilibration after Vacuum Impregnation showing that after restoration of atmospheric pressure in the solid-liquid system, there was a reminding internal low pressure in the apple tissue that slowly increases until reaching the atmospheric pressure, in a time scale that depends on the vacuum applied during the vacuum step. The physiological response of apple tissue on Vacuum Impregnation process was studied indicating the possibility of vesicular transport within the cells. Finally, the possibility to extend the freezing tolerance of strawberry fruits impregnated with cryoprotectants was proven.

Thermodynamics of aqueous biopolymer solutions and fractionation of Dextran

Flory-Huggins interaction parameters and thermal diffusion coefficients were measured for aqueous biopolymer solutions. Dextran (a water soluble polysaccharide) and bovine serum albumin (BSA, a water soluble protein) were used for this study. The former polymer is representative for chain macromolecules and the latter is for globular macromolecules. The interaction parameters for the systems water/dextran and water/BSA were determined as a function of composition by means of vapor pressure measurements, using a combination of headspace sampling and gas chromatography (HS-GC). A new theoretical approach, accounting for chain connectivity and conformational variability, describes the observed dependencies quantitatively for the system water/dextran and qualitatively for the system water/BSA. The phase diagrams of the ternary systems water/methanol/dextran and water/dextran/BSA were determined via cloud point measurements and modeled by means of the direct minimization of the Gibbs energy using the information on the binary subsystems as input parameters. The thermal diffusion of dextran was studied for aqueous solutions in the temperature range 15 < T < 55 oC. The effects of the addition of urea were also studied. In the absence of urea, the Soret coefficient ST changes its sign as T is varied; it is positive for T > 45.0 oC, but negative for T < 45.0 oC. The positive sign of ST means that the dextran molecules migrate towards the cold side of the fluid; this behavior is typical for polymer solutions. While a negative sign indicates the macromolecules move toward the hot side; this behavior has so far not been observed with any other binary aqueous polymer solutions. The addition of urea to the aqueous solution of dextran increases ST and reduces the inversion temperature. For 2 M urea, the change in the sign of ST is observed at T = 29.7 oC. At higher temperature ST is always positive in the studied temperature range. To rationalize these observations it is assumed that the addition of urea opens hydrogen bonds, similar to that induced by an increase in temperature. For a future extension of the thermodynamic studies to the effects of poly-dispersity, dextran was fractionated by means of a recently developed technique called Continuous Spin Fractionation (CSF). The solvent/precipitant/polymer system used for the thermodynamic studies served as the basis for the fractionation of dextran The starting polymer had a weight average molar mass Mw = 11.1 kg/mol and a molecular non-uniformity U= Mw / Mn -1= 1.0. Seventy grams of dextran were fractionated using water as the solvent and methanol as the precipitant. Five fractionation steps yielded four samples with Mw values between 4.36 and 18.2 kg/mol and U values ranging from 0.28 to 0.48.

Numerical investigation of turbulent/non-turbulent interface

The subject of this work is the diffusion of turbulence in a non-turbulent flow. Such phenomenon can be found in almost every practical case of turbulent flow: all types of shear flows (wakes, jet, boundary layers) present some boundary between turbulence and the non-turbulent surround; all transients from a laminar flow to turbulence must account for turbulent diffusion; mixing of flows often involve the injection of a turbulent solution in a non-turbulent fluid. The mechanism of what Phillips defined as “the erosion by turbulence of the underlying non-turbulent flow”, is called entrainment. It is usually considered to operate on two scales with different mechanics. The small scale nibbling, which is the entrainment of fluid by viscous diffusion of turbulence, and the large scale engulfment, which entraps large volume of flow to be “digested” subsequently by viscous diffusion. The exact role of each of them in the overall entrainment rate is still not well understood, as it is the interplay between these two mechanics of diffusion. It is anyway accepted that the entrainment rate scales with large properties of the flow, while is not understood how the large scale inertial behavior can affect an intrinsically viscous phenomenon as diffusion of vorticity. In the present work we will address then the problem of turbulent diffusion through pseudo-spectral DNS simulations of the interface between a volume of decaying turbulence and quiescent flow. Such simulations will give us first hand measures of velocity, vorticity and strains fields at the interface; moreover the framework of unforced decaying turbulence will permit to study both spatial and temporal evolution of such fields. The analysis will evidence that for this kind of flows the overall production of enstrophy , i.e. the square of vorticity omega^2 , is dominated near the interface by the local inertial transport of “fresh vorticity” coming from the turbulent flow. Viscous diffusion instead plays a major role in enstrophy production in the outbound of the interface, where the nibbling process is dominant. The data from our simulation seems to confirm the theory of an inertially stirred viscous phenomenon proposed by others authors before and provides new data about the inertial diffusion of turbulence across the interface.

Evaluation of Microbial Contamination in Bivalve Mollusks: Epidemiology and Diagnosis

Shellfish are filter-feeding organisms that can accumulate many bacteria and viruses. Considering that depuration procedures are not effective in removal of certain microorganisms, shellfish-borne diseases are frequent in many parts of the world, and their control must rely primarily on investigation of prevalence of human pathogens in shellfish and water environment. However, the diffusion of enteric viruses and Vibrio bacteria is not known in many geographical areas, for example in Sardinia, Italy. A survey aimed at investigating the prevalence of Norovirus (NoV), hepatitis A virus (HAV), V. parahaemolyticus, V. cholerae and V. vulnificus was carried out, analyzing both local and imported purified, non-purified and retail shellfish from North Italy and Sardinia. Shellfish from both areas were found contaminated by NoVs, HAV and Vibrio, including retail and purified animals. Molecular analysis evidenced different NoV genogroups and genotypes, including bovine NoVs, as well as pathogenic Vibrio strains, underlining the risk for shellfish consumers. However, also other approaches are needed to control the diffusion of shellfish-borne diseases. It was originally thought that enteric viruses are passively accumulated by shellfish. Recently, it was proven that NoVs bind to specific carbohydrate ligands in oysters, and various NoV strains are characterized by a different bioaccumulation pattern. To deepen the knowledge on this argument, a study was carried out, analyzing bioaccumulation of up to 8 different NoV strains in four different species of shellfish. Different bioaccumulation patterns were observed for each shellfish species and NoV strain used, potentially important in setting up effective shellfish purification protocols. Finally, a novel study of evaluation of viral contamination in shellfish from the French Atlantic coast was carried out following the passage of Xynthia tempest over Western Europe which caused massive destruction. Different enteric viruses were found over a one month period, evidencing the potential of these events of contaminating shellfish.

Outdoor bronze conservation: assessment of protective treatments by accelerated aging and of treatment removal procedures by laser cleaning

Outdoor bronzes exposed to the environment form naturally a layer called patina, which may be able to protect the metallic substrate. However, since the last century, with the appearance of acid rains, a strong change in the nature and properties of the copper based patinas occurred [1]. Studies and general observations have established that bronze corrosion patinas created by acid rain are not only disfiguring in terms of loss of detail and homogeneity, but are also unstable [2]. The unstable patina is partially leached away by rainwater. This leaching is represented by green streaking on bronze monuments [3]. Because of the instability of the patina, conservation techniques are usually required. On a bronze object exposed to the outdoor environment, there are different actions of the rainfall and other atmospheric agents as a function of the monument shape. In fact, we recognize sheltered and unsheltered areas as regards exposure to rainwater [4]. As a consequence of these different actions, two main patina types are formed on monuments exposed to the outdoor environment. These patinas have different electrochemical, morphological and compositional characteristics [1]. In the case of sheltered areas, the patina contains mainly copper products, stratified above a layer strongly enriched in insoluble Sn oxides, located at the interface with the uncorroded metal. Moreover, different colors of the patina result from the exposure geometry. The surface color may be pale green for unsheltered areas, and green and mat black for sheltered areas [4]. Thus, in real outdoor bronze monuments, the corrosion behavior is strongly influenced by the exposure geometry. This must be taken into account when designing conservation procedures, since the patina is in most cases the support on which corrosion inhibitors are applied. Presently, for protecting outdoor bronzes against atmospheric corrosion, inhibitors and protective treatments are used. BTA and its derivatives, which are the most common inhibitors used for copper and its alloy, were found to be toxic for the environment and human health [5, 6]. Moreover, it has been demonstrated that BTA is efficient when applied on bare copper but not as efficient when applied on bare bronze [7]. Thus it was necessary to find alternative compounds. Silane-based inhibitors (already successfully tested on copper and other metallic substrates [8]), were taken into consideration as a non-toxic, environmentally friendly alternative to BTA derivatives for bronze protection. The purpose of this thesis was based on the assessment of the efficiency of a selected compound, to protect the bronze against corrosion, which is the 3-mercapto-propyl-trimethoxy-silane (PropS-SH). It was selected thanks to the collaboration with the Corrosion Studies Centre “Aldo Daccò” at the Università di Ferrara. Since previous studies [9, 10, 11] demonstrated that the addition of nanoparticles to silane-based inhibitors leads to an increase of the protective efficiency, we also wanted to evaluate the influence of the addition of CeO2, La2O3, TiO2 nanoparticles on the protective efficiency of 3-mercapto-propyl-trimethoxy-silane, applied on pre-patinated bronze surfaces. This study is the first section of the thesis. Since restorers have to work on patinated bronzes and not on bare metal (except for contemporary art), it is important to be able to recreate the patina, under laboratory conditions, either in sheltered or unsheltered conditions to test the coating and to obtain reliable results. Therefore, at the University of Bologna, different devices have been designed to simulate the real outdoor conditions and to create a patina which is representative of real application conditions of inhibitor or protective treatments. In particular, accelerated ageing devices by wet & dry (simulating the action of stagnant rain in sheltered areas [12]) and by dropping (simulating the leaching action of the rain in unsheltered areas [1]) tests were used. In the present work, we used the dropping test as a method to produce pre-patinated bronze surfaces for the application of a candidate inhibitor as well as for evaluating its protective efficiency on aged bronze (unsheltered areas). In this thesis, gilded bronzes were also studied. When they are exposed to the outside environment, a corrosion phenomenon appears which is due to the electrochemical couple gold/copper where copper is the anode. In the presence of an electrolyte, this phenomenon results in the formation of corrosion products than will cause a blistering of the gold (or a break-up and loss of the film in some cases). Moreover, because of the diffusion of the copper salts to the surface, aggregates and a greenish film will be formed on the surface of the sample [13]. By coating gilded samples with PropS-SH and PropS-SH containing nano-particles and carrying out accelerated ageing by the dropping test, a discussion is possible on the effectiveness of this coating, either with nano-particles or not, against the corrosion process. This part is the section 2 of this thesis. Finally, a discussion about laser treatment aiming at the assessment of reversibility/re-applicability of the PropS-SH coating can be found in section 3 of this thesis. Because the protective layer loses its efficiency with time, it is necessary to find a way of removing the silane layer, before applying a new one on the “bare” patina. One request is to minimize the damages that a laser treatment would create on the patina. Therefore, different laser fluences (energy/surface) were applied on the sample surface during the treatment process in order to find the best range of fluence. In particular, we made a characterization of surfaces before and after removal of PropS-SH (applied on a naturally patinated surface, and subsequently aged by natural exposure) with laser methods. The laser removal treatment was done by the CNR Institute of Applied Physics “Nello Carrara” of Sesto Fiorentino in Florence. In all the three sections of the thesis, a range of non-destructive spectroscopic methods (Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), μ-Raman spectroscopy, X-Ray diffractometry (XRD)) were used for characterizing the corroded surfaces. AAS (Atomic Absorption Spectroscopy) was used to analyze the ageing solutions from the dropping test in sections 1 and 2.

Physiological and structural aspects of fruit and vegetable mild processing

Over the past years fruit and vegetable industry has become interested in the application of both osmotic dehydration and vacuum impregnation as mild technologies because of their low temperature and energy requirements. Osmotic dehydration is a partial dewatering process by immersion of cellular tissue in hypertonic solution. The diffusion of water from the vegetable tissue to the solution is usually accompanied by the simultaneous solutes counter-diffusion into the tissue. Vacuum impregnation is a unit operation in which porous products are immersed in a solution and subjected to a two-steps pressure change. The first step (vacuum increase) consists of the reduction of the pressure in a solid-liquid system and the gas in the product pores is expanded, partially flowing out. When the atmospheric pressure is restored (second step), the residual gas in the pores compresses and the external liquid flows into the pores. This unit operation allows introducing specific solutes in the tissue, e.g. antioxidants, pH regulators, preservatives, cryoprotectancts. Fruit and vegetable interact dynamically with the environment and the present study attempts to enhance our understanding on the structural, physico-chemical and metabolic changes of plant tissues upon the application of technological processes (osmotic dehydration and vacuum impregnation), by following a multianalytical approach. Macro (low-frequency nuclear magnetic resonance), micro (light microscopy) and ultrastructural (transmission electron microscopy) measurements combined with textural and differential scanning calorimetry analysis allowed evaluating the effects of individual osmotic dehydration or vacuum impregnation processes on (i) the interaction between air and liquid in real plant tissues, (ii) the plant tissue water state and (iii) the cell compartments. Isothermal calorimetry, respiration and photosynthesis determinations led to investigate the metabolic changes upon the application of osmotic dehydration or vacuum impregnation. The proposed multianalytical approach should enable both better designs of processing technologies and estimations of their effects on tissue.

Diffusion in polymer systems studied by fluorescence correlation spectroscopy

Fluorescence correlation spectroscopy (FCS) is a powerful technique to determine the diffusion of fluorescence molecules in various environments. The technique is based on detecting and analyzing the fluctuation of fluorescence light emitted by fluorescence species diffusing through a small and fixed observation volume, formed by a laser focused into the sample. Because of its great potential and high versatility in addressing the diffusion and transport properties in complex systems, FCS has been successfully applied to a great variety of systems. In my thesis, I focused on the application of FCS to study the diffusion of fluorescence molecules in organic environments, especially in polymer melts. In order to examine our FCS setup and a developed measurement protocol, I first utilized FCS to measure tracer diffusion in polystyrene (PS) solutions, for which abundance data exist in the literature. I studied molecular and polymeric tracer diffusion in polystyrene solutions over a broad range of concentrations and different tracer and matrix molecular weights (Mw). Then FCS was further established to study tracer dynamics in polymer melts. In this part I investigated the diffusion of molecular tracers in linear flexible polymer melts [polydimethylsiloxane (PDMS), polyisoprene (PI)], a miscible polymer blend [PI and poly vinyl ethylene (PVE)], and star-shaped polymer [3-arm star polyisoprene (SPI)]. The effects of tracer sizes, polymer Mw, polymer types, and temperature on the diffusion coefficients of small tracers were discussed. The distinct topology of the host polymer, i.e. star polymer melt, revealed the notably different motion of the small tracer, as compared to its linear counterpart. Finally, I emphasized the advantage of the small observation volume which allowed FCS to investigate the tracer diffusions in heterogeneous systems; a swollen cross-linked PS bead and silica inverse opals, where high spatial resolution technique was required.

Characterization of structure and dynamics of submicrometric systems via fluorescence correlation spectroscopy

The presented thesis revolves around the study of thermally-responsive PNIPAAm-based hydrogels in water/based environments, as studied by Fluorescence Correlation Spectroscopy (FCS).rnThe goal of the project was the engineering of PNIPAAm gels into biosensors. Specifically, a gamma of such gels were both investigated concerning their dynamics and structure at the nanometer scale, and their performance in retaining bound bodies upon thermal collapse (which PNIPAAm undergoes upon heating above 32 ºC).rnFCS’s requirements, as a technique, match the limitations imposed by the system. Namely, the need to intimately probe a system in a solvent, which was also fragile and easy to alter. FCS, on the other hand, both requires a fluid environment to work, and is based on the observation of diffusion of fluorescents at nanomolar concentrations. FCS was applied to probe the hydrogels on the nanometer size with minimal invasivity.rnVariables in the gels were addressed in the project including crosslinking degree; structural changes during thermal collapse; behavior in different buffers; the possibility of decreasing the degree of inhomogeneity; behavior of differently sized probes; and the effectiveness of antibody functionalization upon thermal collapse.rnThe evidenced results included the heightening of structural inhomogeneities during thermal collapse and under different buffer conditions; the use of annealing to decrease the inhomogeneity degree; the use of differently sized probes to address different length scale of the gel; and the successful functionalization before and after collapse.rnThe thesis also addresses two side projects, also carried forward via FCS. One, diffusion in inverse opals, produced a predictive simulation model for diffusion of bodies in confined systems as dependent on the bodies’ size versus the characteristic sizes of the system. The other was the observation of interaction of bodies of opposite charge in a water solution, resulting in a phenomenological theory and an evaluation method for both the average residence time of the different bodies together, and their attachment likelihood.

Quality of Service in Distributed Stream Processing for large scale Smart Pervasive Environments

The wide diffusion of cheap, small, and portable sensors integrated in an unprecedented large variety of devices and the availability of almost ubiquitous Internet connectivity make it possible to collect an unprecedented amount of real time information about the environment we live in. These data streams, if properly and timely analyzed, can be exploited to build new intelligent and pervasive services that have the potential of improving people's quality of life in a variety of cross concerning domains such as entertainment, health-care, or energy management. The large heterogeneity of application domains, however, calls for a middleware-level infrastructure that can effectively support their different quality requirements. In this thesis we study the challenges related to the provisioning of differentiated quality-of-service (QoS) during the processing of data streams produced in pervasive environments. We analyze the trade-offs between guaranteed quality, cost, and scalability in streams distribution and processing by surveying existing state-of-the-art solutions and identifying and exploring their weaknesses. We propose an original model for QoS-centric distributed stream processing in data centers and we present Quasit, its prototype implementation offering a scalable and extensible platform that can be used by researchers to implement and validate novel QoS-enforcement mechanisms. To support our study, we also explore an original class of weaker quality guarantees that can reduce costs when application semantics do not require strict quality enforcement. We validate the effectiveness of this idea in a practical use-case scenario that investigates partial fault-tolerance policies in stream processing by performing a large experimental study on the prototype of our novel LAAR dynamic replication technique. Our modeling, prototyping, and experimental work demonstrates that, by providing data distribution and processing middleware with application-level knowledge of the different quality requirements associated to different pervasive data flows, it is possible to improve system scalability while reducing costs.

Polymeric membranes for CO2 separation: effect of aging, humidity and facilitated transport

Polymeric membranes represent a promising technology for gas separation processes, thanks to low costs, reduced energy consumption and limited waste production. The present thesis aims at studying the transport properties of two membrane materials, suitable for CO2 purification applications. In the first part, a polyimide, Matrimid 5218, has been throughout investigated, with particular reference to the effect of thermal treatment, aging and the presence of water vapor in the gas transport process. Permeability measurements showed that thermal history affects relevantly the diffusion of gas molecules across the membrane, influencing also the stability of the separation performances. Subsequently, the effect of water on Matrimid transport properties has been characterized for a wide set of incondensable penetrants. A monotonous reduction of permeability took place at increasing the water concentration within the polymer matrix, affecting the investigated gaseous species to the same extent, despite the different thermodynamic and kinetic features. In this view, a novel empirical model, based on the Free Volume Theory, has been proposed to qualitatively describe the phenomenon. Moreover, according to the accurate representation of the experimental data, the suggested approach has been combined with a more rigorous thermodynamic tool (NELF Model), allowing an exhaustive description of water influence on the single parameters contributing to the gas permeation across the membrane. In the second part, the study has focused on the synthesis and characterization of facilitated transport membranes, able to achieving outstanding separation performances thanks to the chemical enhancement of CO2 permeability. In particular, the transport properties have been investigated for high pressure CO2 separation applications and specific solutions have been proposed to solve stability issues, frequently arising under such severe conditions. Finally, the effect of different process parameters have been investigated, aiming at the identification of the optimal conditions capable to maximize the separation performance.

Describing and explaining the foreign expansion of network managing electronic business companies (NM-EBCs)

This study deals with the internationalization behavior of a new and specific type of e-business company, namely the network managing e-business company (NM-EBC). The business model of such e-business companies is based on providing a platform and applications for users to connect and interact, on gathering and channeling the inputs provided by the users, and on organizing and managing the cross-relationships of the various participants. Examples are online communities, matching platforms, and portals. Since NM-EBCs internationalize by replicating their business model in a foreign market and by building up and managing a network of users, who provide input themselves and interact with each other, they have to convince users in foreign markets to join the network and hence to adopt their platform. We draw upon Rogers’ Diffusion of Innovations Theory and Network Theory to explain the internationalization behavior of NM-EBCs. These two theories originate from neighboring disciplines and have not yet been used to explain the internationalization of firms. We combine both theories and formulate hypotheses about which strategies NM-EBCs may choose to expand abroad. To test the applicability of our theory and to gain rich data about the internationalization behavior of these firms, we carried out multiple case studies with internationally active Germany-based NM-EBCs.

Tracer diffusion at water-oil interfaces studied by fluorescence correlation spectroscopy

The adsorption of particles and surfactants at water-oil interfaces has attracted continuous attention because of its emulsion stabilizing effect and the possibility to form two-dimensional materials. Herein, I studied the interfacial diffusion of single molecules and nanoparticles at water-oil interfaces using fluorescence correlation spectroscopy. rnrnFluorescence correlation spectroscopy (FCS) is a promising technique to study diffusion of fluorescent tracers in diverse conditions. This technique monitors and analyzes the fluorescence fluctuation caused by single fluorescent tracers coming in and out of a diffraction-limited observation volume “one at a time”. Thus, this technique allows a combination of high precision, high spatial resolution and low tracer concentration. rnrnIn chapter 1, I discussed some controversial questions regarding the properties of water-hydrophobic interfaces and also introduced the current progress on the stability and dynamic of single nanoparticles at water-oil interfaces. The materials and setups I used in this thesis were summarized in chapter 2. rnrnIn chapter 3, I presented a new strategy to study the properties of water-oil interfaces. The two-dimensional diffusion of isolated molecular tracers at water/n-alkane interfaces was measured using fluorescence correlation spectroscopy. The diffusion coefficients of larger tracers with a hydrodynamic radius of 4.0 nm agreed well with the values calculated from the macroscopic viscosities of the two bulk phases. However, for small molecule tracers with hydrodynamic radii of only 1.0 and 0.6 nm, notable deviations were observed, indicating the existence of an interfacial region with a reduced effective viscosity. rnrnIn chapter 4, the interfacial diffusion of nanoparticles at water-oil interfaces was investigated using FCS. In stark contrast to the interfacial diffusion of molecular tracers, that of nanoparticles at any conditions is slower than the values calculated in accordance to the surrounding viscosity. The diffusion of nanoparticles at water-oil interfaces depended on the interfacial tension of liquid-liquid interfaces, the surface properties of nanoparticles, the particle sizes and the viscosities of surrounding liquid phases. In addition, the interfacial diffusion of nanoparticles with Janus motif is even slower than that of their symmetric counterparts. Based on the experimental results I obtained, I drew some possibilities to describe the origin of nanoparticle slowdown at water-oil interfaces.

Diffusion in heterogeneous systems studied by laser scanning confocal microscopy and fluorescence correlation spectroscopy

Understanding and controlling the mechanism of the diffusion of small molecules, macromolecules and nanoparticles in heterogeneous environments is of paramount fundamental and technological importance. The aim of the thesis is to show, how by studying the tracer diffusion in complex systems, one can obtain information about the tracer itself, and the system where the tracer is diffusing. rnIn the first part of my thesis I will introduce the Fluorescence Correlation Spectroscopy (FCS) which is a powerful tool to investigate the diffusion of fluorescent species in various environments. By using the main advantage of FCS namely the very small probing volume (<1µm3) I was able to track the kinetics of phase separation in polymer blends at late stages by looking on the molecular tracer diffusion in individual domains of the heterogeneous structure of the blend. The phase separation process at intermediate stages was monitored with laser scanning confocal microscopy (LSCM) in real time providing images of droplet coalescence and growth. rnIn a further project described in my thesis I will show that even when the length scale of the heterogeneities becomes smaller than the FCS probing volume one can still obtain important microscopic information by studying small tracer diffusion. To do so, I will introduce a system of star shaped polymer solutions and will demonstrate that the mobility of small molecular tracers on microscopic level is nearly not affected by the transition of the polymer system to a “glassy” macroscopic state. rnIn the last part of the thesis I will introduce and describe a new stimuli responsive system which I have developed, that combines two levels of nanoporosity. The system is based on poly-N-isopropylacrylamide (PNIPAM) and silica inverse opals (iOpals), and allows controlling the diffusion of tracer molecules. rn

Formation and surface exchange of nitrous acid

Die salpetrige Säure (HONO) ist eine der reaktiven Stickstoffkomponenten der Atmosphäre und Pedosphäre. Die genauen Bildungswege von HONO, sowie der gegenseitige Austausch von HONO zwischen Atmosphäre und Pedosphäre sind noch nicht vollständig aufgedeckt. Bei der HONO-Photolyse entsteht das Hydroxylradikal (OH) und Stickstoffmonooxid (NO), was die Bedeutsamkeit von HONO für die atmosphärische Photochemie widerspiegelt.rnUm die genannte Bildung von HONO im Boden und dessen anschließenden Austausch mit der Atmosphäre zu untersuchen, wurden Messungen von Bodenproben mit dynamischen Kammern durchgeführt. Im Labor gemessene Emissionsflüsse von Wasser, NO und HONO zeigen, dass die Emission von HONO in vergleichbarem Umfang und im gleichen Bodenfeuchtebereich wie die für NO (von 6.5 bis 56.0 % WHC) stattfindet. Die Höhe der HONO-Emissionsflüsse bei neutralen bis basischen pH-Werten und die Aktivierungsenergie der HONO-Emissionsflüsse führen zu der Annahme, dass die mikrobielle Nitrifikation die Hauptquelle für die HONO-Emission darstellt. Inhibierungsexperimente mit einer Bodenprobe und die Messung einer Reinkultur von Nitrosomonas europaea bestärkten diese Theorie. Als Schlussfolgerung wurde das konzeptionelle Model der Bodenemission verschiedener Stickstoffkomponenten in Abhängigkeit von dem Wasserhaushalt des Bodens für HONO erweitert.rnIn einem weiteren Versuch wurde zum Spülen der dynamischen Kammer Luft mit erhöhtem Mischungsverhältnis von HONO verwendet. Die Messung einer hervorragend charakterisierten Bodenprobe zeigte bidirektionale Flüsse von HONO. Somit können Böden nicht nur als HONO-Quelle, sondern auch je nach Bedingungen als effektive Senke dienen. rnAußerdem konnte gezeigt werden, dass das Verhältnis von HONO- zu NO-Emissionen mit dem pH-Wert des Bodens korreliert. Grund könnte die erhöhte Reaktivität von HONO bei niedrigem pH-Wert und die längere Aufenthaltsdauer von HONO verursacht durch reduzierte Gasdiffusion im Bodenporenraum sein, da ein niedriger pH-Wert mit erhöhter Bodenfeuchte am Maximum der Emission einhergeht. Es konnte gezeigt werden, dass die effektive Diffusion von Gasen im Bodenporenraum und die effektive Diffusion von Ionen in der Bodenlösung die HONO-Produktion und den Austausch von HONO mit der Atmosphäre begrenzen. rnErgänzend zu den Messungen im Labor wurde HONO während der Messkampagne HUMPPA-COPEC 2010 im borealen Nadelwald simultan in der Höhe von 1 m über dem Boden und 2 bis 3 m über dem Blätterdach gemessen. Die Budgetberechnungen für HONO zeigen, dass für HONO sämtliche bekannte Quellen und Senken in Bezug auf die übermächtige HONO-Photolyserate tagsüber vernachlässigbar sind (< 20%). Weder Bodenemissionen von HONO, noch die Photolyse von an Oberflächen adsorbierter Salpetersäure können die fehlende Quelle erklären. Die lichtinduzierte Reduktion von Stickstoffdioxid (NO2) an Oberflächen konnte nicht ausgeschlossen werden. Es zeigte sich jedoch, dass die fehlende Quelle stärker mit der HONO-Photolyserate korreliert als mit der entsprechenden Photolysefrequenz, die proportional zur Photolysefrequenz von NO2 ist. Somit lässt sich schlussfolgern, dass entweder die Photolyserate von HONO überschätzt wird oder dass immer noch eine unbekannte, HONO-Quelle existiert, die mit der Photolyserate sehr stark korreliert. rn rn