| 1. |
- Halldin Stenlid, Joakim, 1987-
(författare)
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Computational Studies of Chemical Interactions: Molecules, Surfaces and Copper Corrosion
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The chemical bond – a corner stone in science and a prerequisite for life – is the focus of this thesis. Fundamental and applied aspects of chemical bonding are covered including the development of new computational methods for the characterization and rationalization of chemical interactions. The thesis also covers the study of corrosion of copper-based materials. The latter is motivated by the proposed use of copper as encapsulating material for spent nuclear fuel in Sweden.In close collaboration with experimental groups, state-of-the-art computational methods were employed for the study of chemistry at the atomic scale. First, oxidation of nanoparticulate copper was examined in anoxic aqueous media in order to better understand the copper-water thermodynamics in relation to the corrosion of copper material under oxygen free conditions. With a similar ambition, the water-cuprite interface was investigated with regards to its chemical composition and reactivity. This was compared to the behavior of methanol and hydrogen sulfide at the cuprite surface.An overall ambition during the development of computational methods for the analysis of chemical bonding was to bridge the gap between molecular and materials chemistry. Theory and results are thus presented and applied in both a molecular and a solid-state framework. A new property, the local electron attachment energy, for the characterization of a compound’s local electrophilicity was introduced. Together with the surface electrostatic potential, the new property predicts and rationalizes regioselectivity and trends of molecular reactions, and interactions on metal and oxide nanoparticles and extended surfaces.Detailed atomistic understanding of chemical processes is a prerequisite for the efficient development of chemistry. We therefore envisage that the results of this thesis will find widespread use in areas such as heterogeneous catalysis, drug discovery, and nanotechnology.
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| 4. |
- Trpevski, Daniel
(författare)
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Models of Corticostriatal Synaptic Plasticity and Plateau Potentials in Striatal Projection Neurons
- 2024
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis we studied synaptic plasticity and neuronal computation in single striatal projection neurons (SPNs), which have a major role in goal-directed learning. Goal-directed or reward learning means to learn, based on sensory information from the body and the environment, to select actions out of all the behavioral repertoire that lead to obtaining a goal or reward (such as food or water). In mammals, all the behavioral motor repertoire is under constant, tonic inhibition, and the direct-pathway SPNs (dSPNs) select (disinhibit) goal-obtaining actions. The learning process is guided by the neuromodulator dopamine which signals the positive or negative out-come of an action. The synapses from cortical neurons on to the dSPNs, called corticostriatal synapses, are responsive to dopamine signals, and can strengthen and weaken based on the (positive or negative) action outcome. This promotes or discourages future actions in the same or similar sensory context.Within a collaborative computational modeling effort, we studied the biochemical circuitry in the corticostriatal synapses with multiscale modeling and simulations. This circuitry in the corticostriatal synapses responds to neuromodulatory signals and controls the expression of synaptic plasticity. Multiscale modeling and simulations enable studying a system at multiple temporal and spatial scales, and integrating the results across the different scales. Based on molecular dynamics simulations of the enzyme which transduces extracellular neuromodulatory signals into an intracellular second messenger molecule, and Brownian dynamics simulations of regulator molecules binding to the enzyme, we constructed a kinetic model ofthe enzyme-based signal transduction network. The kinetic model showed that two co-occuring neuromodulatory signals, a dopamine peak and an acetylcholine pause, are required to produce the second messenger and thus enable strengthening of corticostriatal synapses onto dSPNs, and that only the dopamine signal is not enough.Next, we developed a local, calcium- and reward-dependent learning rule based on what is known about the biochemical circuitry of corticostriatalsynapses onto dSPNs. We show that with this biologically-based learning rule, single SPNs can learn to solve the nonlinear feature binding problem(NFBP), a computationally hard problem representing the class of linearly nonseparable tasks. This result suggests that different, unrelated or partially related stimuli that require executing the same action to obtain a goal, canuse the same SPNs responsible for selecting that action, and that a single SPN can reliably distinguish between similar stimuli.The solution of the NFBP with the aforementioned learning rule relieson supralinear dendritic voltage elevations called plateau potentials. Experimentally, plateau potentials are all-or-none events, a property crucial for performing nonlinear computations required to solve the NFBP. However, computational models of plateau potentials often produce graded voltage elevations. We analyzed and compared existing plateau potential models, and found that long-lasting glutamate spillover in the extrasynaptic space robustly produces all-or-none plateau potentials by activating extrasynaptic N-methyl-D-aspartate (NMDA) glutamate receptors. This suggests that glutamate spillover may be a mechanism for generating all-or-none plateau potentials in vivo, as well.In summary, the findings presented in this thesis advance our understanding of the role of single dSPNs in goal-directed learning, the biophysical mechanisms involved in performing their nonlinear computations, and the neuromodulatory signals necessary to produce synaptic strengthening and thus implement goal-directed learning.
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| 5. |
- Axelsson, Karolin
(författare)
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Chemical signals in interactions between Hylobius abietis and associated bacteria
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The pine weevil (Hylobius abietis L.) is one of the two topmost economically important insect pests in Swedish conifer forests. The damage increase in areas were the silvicultural practice is to use clear cuttings were the insects gather and breed. During egglaying the female protects her offspring by creating a cave in roots and stumps were she puts her egg and covers it with frass, a mixture of weevil feces and chewed bark. Adult pine weevils have been observed to feed on the other side of the egg laying site and antifeedant substance has been discovered in the feces of the pine weevil. We think it is possible that microorganisms present in the frass contribute with antifeedant/repellent substances. Little is known about the pine weevils associated bacteria community and their symbiotic functions. In this thesis the bacterial community is characterized in gut and frass both from pine weevils in different populations across Europe as well as after a 28 day long diet regime on Scots pine, silver birch or bilberry. Volatile substances produced by isolated bacteria as well as from a consortium of microorganisms were collected with solid phase micro extraction (SPME) and analyzed with GC-MS. The main volatiles were tested against pine weevils using a two-choice test. Wolbachia, Rahnella aquatilis, Serratia and Pseudomonas syringae was commonly associated with the pine weevil. 2-Methoxyphenol, 2-phenylethanol, 3-methyl-1-butanol were found in the headspace from Rahnella aquatilis when grown in substrate containing pine bark. 2-Methoxyphenol and 3-methyl-1-butanol, phenol and methyl salicylate were found in pine feces. Birch and bilberry feces emitted mainly linalool oxides and bilberry emitted also small amounts of 2-phenylethanol.A second part of the thesis discusses the role of fungi in forest insect interactions and the production of oxygenated monoterpenes as possible antifeedants. Spruce bark beetles (Ips typhographus L.) aggregate with the help of pheromones and with collected forces they kill weakened adult trees as a result of associated fungi growth and larval development. A fungi associated with the bark beetle, Grosmannia europhoides, was shown to produce de novo 2-methyl-3-buten-2-ol, the major component of the spruce bark beetle aggregation pheromone. Chemical defense responses against Endoconidiophora polonica and Heterobasidion parviporum were investigated using four clones of Norway spruce with different susceptibility to Heterobasidion sp. Clone specific differences were found in induced mono-, sesqui and diterpenes. A number of oxygenated monoterpenes which are known antifeedants for the pine weevil were produced in the infested areas.
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| 6. |
- Karlsson, Rasmus, 1987-
(författare)
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Theoretical and Experimental Studies of Electrode and Electrolyte Processes in Industrial Electrosynthesis
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Heterogeneous electrocatalysis is the usage of solid materials to decrease the amount of energy needed to produce chemicals using electricity. It is of core importance for modern life, as it enables production of chemicals, such as chlorine gas and sodium chlorate, needed for e.g. materials and pharmaceuticals production. Furthermore, as the need to make a transition to usage of renewable energy sources is growing, the importance for electrocatalysis used for electrolytic production of clean fuels, such as hydrogen, is rising. In this thesis, work aimed at understanding and improving electrocatalysts used for these purposes is presented.A main part of the work has been focused on the selectivity between chlorine gas, or sodium chlorate formation, and parasitic oxygen evolution. An activation of anode surface Ti cations by nearby Ru cations is suggested as a reason for the high chlorine selectivity of the “dimensionally stable anode” (DSA), the standard anode used in industrial chlorine and sodium chlorate production. Furthermore, theoretical methods have been used to screen for dopants that can be used to improve the activity and selectivity of DSA, and several promising candidates have been found. Moreover, the connection between the rate of chlorate formation and the rate of parasitic oxygen evolution, as well as the possible catalytic effects of electrolyte contaminants on parasitic oxygen evolution in the chlorate process, have been studied experimentally.Additionally, the properties of a Co-doped DSA have been studied, and it is found that the doping makes the electrode more active for hydrogen evolution. Finally, the hydrogen evolution reaction on both RuO2 and the noble-metal-free electrocatalyst material MoS2 has been studied using a combination of experimental and theoretically calculated X-ray photoelectron chemical shifts. In this way, insight into structural changes accompanying hydrogen evolution on these materials is obtained.
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| 7. |
- Aas, Erik, et al.
(författare)
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Limiting directions for random walks in classical affine Weyl groups
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Let be a finite Weyl group and the corresponding affine Weyl group. A random element of can be obtained as a reduced random walk on the alcoves of . By a theorem of Lam (Ann. Probab. 2015), such a walk almost surely approaches one of many directions. We compute these directions when is , and and the random walk is weighted by Kac and dual Kac labels. This settles Lam's questions for types and in the affirmative and for type in the negative. The main tool is a combinatorial two row model for a totally asymmetric simple exclusion process called the -TASEP, with four parameters. By specializing the parameters in different ways, we obtain TASEPs for each of the Weyl groups mentioned above. Computing certain correlations in these TASEPs gives the desired limiting directions.
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| 8. |
- Benselfelt, Tobias, 1989-
(författare)
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Design of Cellulose-based Materials by Supramolecular Assemblies
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Due to climate change and plastic pollution, there is an increasing demand for bio-based materials with similar properties to those of common plastics yet biodegradable. In this respect, cellulose is a strong candidate that is already being refined on a large industrial scale, but the properties differ significantly from those of common plastics in terms of shapeability and water-resilience.This thesis investigates how supramolecular interactions can be used to tailor the properties of cellulose-based materials by modifying cellulose surfaces or control the assembly of cellulose nanofibrils (CNFs). Most of the work is a fundamental study on interactions in aqueous environments, but some material concepts are presented and potential applications are discussed.The first part deals with the modification of cellulose by the spontaneous adsorption of xyloglucan or polyelectrolytes. The results indicate that xyloglucan adsorbs to cellulose due to the increased entropy of water released from the surfaces, which is similar to the increased entropy of released counter-ions that drives polyelectrolyte adsorption. The polyelectrolyte adsorption depends on the charge of the cellulose up to a limit after which the charge density affects only the first adsorbed layer in a multilayer formation.Latex nanoparticles with polyelectrolyte coronas can be adsorbed onto cellulose in order to prepare hydrophobic cellulose surfaces with strong and ductile wet adhesion, provided the glass transition of the core is below the ambient temperature.The second part of the thesis seeks to explain the interactions between different types of cellulose nanofibrils in the presence of different ions, using a model consisting of ion-ion correlation and specific ion effects, which can be employed to rationally design water-resilient and transparent nanocellulose films. The addition of small amounts of alginate also creates interpenetrating double networks, and these networks lead to a synergy which improves both the stiffness and the ductility of the films in water.A network model has been developed to understand these materials, with the aim to explain the properties of fibril networks, based on parameters such as the aspect ratio of the fibrils, the solidity of the network, and the ion-induced interactions that increase the friction between fibrils. With the help of this network model and the model for ion-induced interactions, we have created films with wet-strengths surpassing those of common plastics, or a ductility suitable for hygroplastic forming into water-resilient and biodegradable packages. Due to their transparency, water content, and the biocompatibility of cellulose, these materials are also suitable for biomaterial or bioelectronics applications.
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| 9. |
- Lindeberg, Tony, 1964-, et al.
(författare)
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Linear Scale-Space II : Early visual operations
- 1994
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Ingår i: Geometry-Driven Diffusion in Vision. - : Kluwer Academic Publishers. ; , s. 43-77
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Bokkapitel (övrigt vetenskapligt/konstnärligt)abstract
- Vision deals with the problem of deriving information about the world from the light reflected from it. Although the active and task-oriented nature of vision is only implicit in this formulation, this view captures several of the essential aspects of vision. As Marr (1982) phrased it in his book Vision, vision is an information processing task, in which an internal representation of information is of utmost importance. Only by representation information can be captured and made available to decision processes. The purpose of a representation is to make certain aspects of the information content explicit, that is, immediately accessible without any need for additional processing.This introductory chapter deals with a fundamental aspect of early image representation---the notion of scale. As Koenderink (1984) emphasizes, the problem of scale must be faced in any imaging situation. An inherent property of objects in the world and details in images is that they only exist as meaningful entities over certain ranges of scale. A simple example of this is the concept of a branch of a tree, which makes sense only at a scale from, say, a few centimeters to at most a few meters. It is meaningless to discuss the tree concept at the nanometer or the kilometer level. At those scales it is more relevant to talk about the molecules that form the leaves of the tree, or the forest in which the tree grows. Consequently, a multi-scale representation is of crucial importance if one aims at describing the structure of the world, or more specifically the structure of projections of the three-dimensional world onto two-dimensional images.The need for multi-scale representation is well understood, for example, in cartography; maps are produced at different degrees of abstraction. A map of the world contains the largest countries and islands, and possibly, some of the major cities, whereas towns and smaller islands appear at first in a map of a country. In a city guide, the level of abstraction is changed considerably to include streets and buildings etc. In other words, maps constitute symbolic multi-scale representations of the world around us, although constructed manually and with very specific purposes in mind.To compute any type of representation from image data, it is necessary to extract information, and hence interact with the data using certain operators. Some of the most fundamental problems in low-level vision and image analysis concern: what operators to use, where to apply them, and how large they should be. If these problems are not appropriately addressed, the task of interpreting the output results can be very hard. Ultimately, the task of extracting information from real image data is severely influenced by the inherent measurement problem that real-world structures, in contrast to certain ideal mathematical entities, such as ``points'' or ``lines'', appear in different ways depending upon the scale of observation.Phrasing the problem in this way shows the intimate relation to physics. Any physical observation by necessity has to be done through some finite aperture, and the result will, in general, depend on the aperture of observation. This holds for any device that registers physical entities from the real world including a vision system based on brightness data. Whereas constant size aperture functions may be sufficient in many (controlled) physical applications, e.g., fixed measurement devices, and also the aperture functions of the basic sensors in a camera (or retina) may have to determined a priori because of practical design constraints, it is far from clear that registering data at a fixed level of resolution is sufficient. A vision system for handling objects of different sizes and at difference distances needs a way to control the scale(s) at which the world is observed.The goal of this chapter is to review some fundamental results concerning a framework known as scale-space that has been developed by the computer vision community for controlling the scale of observation and representing the multi-scale nature of image data. Starting from a set of basic constraints (axioms) on the first stages of visual processing it will be shown that under reasonable conditions it is possible to substantially restrict the class of possible operations and to derive a (unique) set of weighting profiles for the aperture functions. In fact, the operators that are obtained bear qualitative similarities to receptive fields at the very earliest stages of (human) visual processing (Koenderink 1992). We shall mainly be concerned with the operations that are performed directly on raw image data by the processing modules are collectively termed the visual front-end. The purpose of this processing is to register the information on the retina, and to make important aspects of it explicit that are to be used in later stage processes. If the operations are to be local, they have to preserve the topology at the retina; for this reason the processing can be termed retinotopic processing.Early visual operationsAn obvious problem concerns what information should be extracted and what computations should be performed at these levels. Is any type of operation feasible? An axiomatic approach that has been adopted in order to restrict the space of possibilities is to assume that the very first stages of visual processing should be able to function without any direct knowledge about what can be expected to be in the scene. As a consequence, the first stages of visual processing should be as uncommitted and make as few irreversible decisions or choices as possible.The Euclidean nature of the world around us and the perspective mapping onto images impose natural constraints on a visual system. Objects move rigidly, the illumination varies, the size of objects at the retina changes with the depth from the eye, view directions may change etc. Hence, it is natural to require early visual operations to be unaffected by certain primitive transformations (e.g. translations, rotations, and grey-scale transformations). In other words, the visual system should extract properties that are invariant with respect to these transformations.As we shall see below, these constraints leads to operations that correspond to spatio-temporal derivatives which are then used for computing (differential) geometric descriptions of the incoming data flow. Based on the output of these operations, in turn, a large number of feature detectors can be expressed as well as modules for computing surface shape.The subject of this chapter is to present a tutorial overview on the historical and current insights of linear scale-space theories as a paradigm for describing the structure of scalar images and as a basis for early vision. For other introductory texts on scale-space; see the monographs by Lindeberg (1991, 1994) and Florack (1993) as well as the overview articles by ter Haar Romeny and Florack (1993) and Lindeberg (1994).
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| 10. |
- White, Jai, 1991-
(författare)
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From Facets to Flow: The Electrooxidation of Glycerol on Pd-based catalysts
- 2023
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Glycerol, a by-product of biodiesel refineries, has uses in industries such as cosmetics, food, and pharmaceuticals. However, its usage is small compared to the amount of glycerol produced from biodiesel production. Therefore, there is an opportunity to use glycerol, an important platform chemical, as a cheap feedstock for the synthesis of valuable chemicals. These chemicals can be formed in aqueous media through the glycerol electrooxidation reaction (GEOR) on the anode with hydrogen gas concurrently generated on the cathode. This thesis focuses on the GEOR in alkaline media on Pd and PdNi catalysts. The works compiled here evaluate the GEOR using electrochemical methods such as cyclic voltammetry, galvanostatic polarisation curves, chronoamperometry and chronopotentiometry. Pd and PdNi catalysts were fabricated through chemical synthesis, and electrodeposition onto Ni substrates. Singularly oriented Pd crystal facets were studied, showing those approximating Pd (111) as the most active. Similarly faceted bimetallic PdNi nanoparticles proved significantly more active than pure Pd. Effects of mass transport, studied for Pd/NiRDE and PdNi/NiRDE, indicated performance effects linked to diffusion and underutilisation of thicker catalyst layers. In aerated solutions, industrially relevant current densities were achieved on PdNi/Nifoam in concentrated electrolytes at elevated temperatures for extended periods. The analysis of glycerol oxidation products, formed during steady state measurements, was done using high performance liquid chromatography. The two major products were consistently shown to be glycerate and lactate. This work, covering many aspects of the GEOR, shows that Pd-based catalysts have potential for future industrial application.
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