| 1. |
- Abdu, Yassir Ahmed Mohamed, 1966-
(författare)
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Mössbauer Spectroscopy of Meteoritic and Synthetic Fe-Ni Alloys
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis reports on the results of investigating Fe-containing minerals in meteorites, with focus on Fe-Ni minerals and their magnetic properties, along with some synthetic Fe-Ni analogues. The New Halfa meteorite, which fell in Sudan 1994, has been studied using Mössbauer spectroscopy, X-ray diffraction, and electron microprobe analysis techniques, and classified as an ordinary L-type chondrite of petrologic type 4. Mössbauer spectra of taenite-enriched samples from the metal particles of the New Halfa (L4) and Al Kidirate (H6) meteorites identify the following γ (fcc) Fe-Ni phases: the ferromagnetic atomically ordered taenite (tetrataenite) with ~ 50 at % Ni, the ferromagnetic disordered taenite with ~ 50 at % Ni, the low-Ni (~ 25 at %) paramagnetic taenite (antitaenite). The presence of the superstructure of tetrataenite is confirmed by synchrotron X-ray diffraction.Fe-rich γ (fcc) Fe-Ni alloys with compositions Fe79Ni21, Fe76Ni24, and Fe73Ni27, which serve as synthetic analogues of antitaenite, are prepared by mechanical alloying and subsequent annealing at 650 °C. The Mössbauer results indicate that these alloys are inhomogeneous and contain a high moment (HM) ferromagnetic Ni-rich phase (> 30 at % Ni) and a low moment (LM) paramagnetic Fe-rich phase, which orders antiferromagnetically at low temperature. The coexistence of these phases is attributed to phase segregation occurring on short range, probably nanometer scale, consistent with the Fe-Ni phase diagram below 400 °C where there is a miscibility gap associated with a spinodal decomposition in alloys with < 50 at % Ni.The combined high field Mössbauer spectroscopy and SQUID magnetometry results on these alloys at room temperature indicate large induced local magnetic moments in the paramagnetic part of the sample, which increases with increasing the Ni content. The results, when compared with the high field Mössbauer results on antitaenite from the metal particle of Al Kidirate and New Halfa meteorites may be used to estimate the Ni content of antitaenite in meteorites.High pressure 57Fe Mössbauer spectroscopy measurements up to ~ 41 GPa have been carried out at room temperature using the diamond anvil cell (DAC) technique in order to investigate the magnetic properties of γ (fcc) 57Fe53Ni47 alloy. The results indicate a pressure induced Invar effect at ~ 7 GPa and a non-magnetic or paramagnetic state above 20 GPa, demonstrating the volume dependence of the magnetic moment of γ (fcc) Fe-Ni alloys.
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| 2. |
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| 3. |
- Abrahamsson, Malin L. A.
(författare)
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Electron Transfer in Ruthenium-Manganese Complexes for Artificial Photosynthesis : Studies in Solution and on Electrode Surfaces
- 2001
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In today’s society there is an increasing need for energy, an increase which for the most part is supplied by the use of fossil fuels. Fossil fuel resources are limited and their use has harmful effects on the environment, therefore the development of technologies that produce clean energy sources is very appealing. Natural photosynthesis is capable of converting solar energy into chemical energy through a series of efficient energy and electron transfer reactions with water as the only electron source. Thus, constructing an artificial system that uses the same principles to convert sunlight into electricity or storable fuels like hydrogen is one of the major forces driving artificial photosynthesis research.This thesis describes supramolecular complexes with the intention of mimicking the electron transfer reactions of the donor side in Photosystem II, where a manganese cluster together with a tyrosine catalyses the oxidation of water. All complexes are based on Ru(II)-trisbipyridine as a photosensitizer that is covalently linked to electron donors like tyrosine or manganese. Photochemical reactions are studied with time-resolved transient absorption and emission measurements. Electrochemical techniques are used to study the electrochemical behavior, and different photoelectrochemical techniques are used to investigate the complexes adsorbed onto titanium dioxide surfaces. In all complexes, intramolecular electron transfer occurs from the linked donor to photo-oxidized Ru(III). It is also observed that coordinated Mn(II) quenches the excited state of Ru(II), a reaction that is found to be distance dependent. However, by modifying one of the complexes, its excited state properties can be tuned in a way that decreases the quenching and keeps the electron transfer properties. The obtained results are of significance for the development of multinuclear Ru-Mn complexes that are capable of multi-electron transfer.
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| 4. |
- Abramson, Jeff
(författare)
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Structural studies on the integral membrane protein, ubiquinol oxidase from Escherichia coli
- 2001
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Heme-copper oxidases are redox-driven proton pumps that couple the reduction of molecular oxygen to water with the vectorial translocation of protons across the membrane. The proton gradient generated by heme-copper oxidases and the other members of the aerobic respiratory chain is ultimately used to drive the synthesis of ATP. There are two main branches of the heme-copper oxidases that are characterized by the electron donating substrate; the cytochrome c oxidases, which use cytochrome c as the electron donor, and the ubiquinol oxidases, which use a lipid-soluble molecule, ubiquinol, as their electron donor. These enzymes share important structural and functional features. This thesis presents the procedures that have led to the first crystal structure of a ubiquinol oxidase, cytochrome bo, oxidase from Escherichia coli, at a resolution of 3.5 Å. The overall structure of the enzyme is similar to those of cytochrome c oxidases; however the membrane spanning region of subunit I contains a cluster of polar residues exposed to the interior of the lipid bilayer. No such structural feature is present in cytochrome c oxidases. Mutagenesis studies on residues in this region strongly suggest that this area forms a ubiquinone binding site. A comparison of this region with known ubiquinone binding sites shows remarkable similarities. In light of these findings specific roles for these polar residues is proposed in electron and proton transfer in ubiquinol oxidase. A fusion protein of cytochrome bo3-Protein Z was generated in an attempt to increase the hydrophilic surface of the protein, thus extending protein-protein contacts within the crystal lattice structure. Such an approach can be used to facilitate crystallization.
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| 5. |
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| 6. |
- Acharya, Parag, 1972-
(författare)
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Studies on the Non-covalent Interactions (Stereoelectronics, Stacking and Hydrogen Bonding) in the Self-assembly of DNA and RNA
- 2003
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis is based on ten publications (Papers I-X). The phosphodiester backbone makes DNA or RNA to behave as polyelectrolyte, the pentose sugar gives the flexibility, and the aglycones promote the self-assembly or the ligand-binding process. The hydrogen bonding, stacking, stereoelectronics and hydration are few of the important non-covalent forces dictating the self-assembly of DNA/RNA. The pH-dependent thermodynamics clearly show (Papers I and II) that a change of the electronic character of aglycone modulates the conformation of the sugar moiety by the tunable interplay of stereoelectronic anomeric and gauche effects, which are further transmitted to steer the sugar-phosphate backbone conformation in a cooperative manner. 3'-anthraniloyl adenosine (a mimic of 3'-teminal CCAOH of the aminoacyl-tRNAPhe) binds to EF-Tu*GTP in preference over 2'-anthraniloyl adenosine, thereby showing (Paper III) that the 2’-endo sugar conformation is a more suitable mimic of the transition state geometry than the 3’-endo conformation in discriminating between correctly and incorrectly charged aminoacyl-tRNAPhe by EF-Tu during protein synthesis. The presence of 2'-OH in RNA distinguishes it from DNA both functionally as well as structurally. This work (Paper IV) provides straightforward NMR evidence to show that the 2'-OH is intramolecularly hydrogen bonded with the vicinal 3'-oxygen, and the exposure of the 3'-phosphate of the ribonucleotides to the bulk water determines the availability of the bound water around the vicinal 2'-OH, which then can play various functional role through inter- or intramolecular interactions. The pH-dependent 1H NMR study with nicotinamide derivatives demonstrates (Paper V) that the cascade of intramolecular cation (pyridinium)-π(phenyl)-CH(methyl) interaction in edge-to-face geometry is responsible for perturbing the pKa of the pyridine-nitrogen as well as for the modulation of the aromatic character of the neighboring phenyl moiety, which is also supported by the T1 relaxation studies and ab initio calculations. It has been found (Papers VI-IX) that the variable intramolecular electrostatic interaction between electronically coupled nearest neighbor nucleobases (steered by their respective microenvironments) can modulate their respective pseudoaromatic characters. The net result of this pseudoaromatic cross-modulation is the creation of a unique set of aglycones in an oligo or polynucleotide, whose physico-chemical properties are completely dependent upon the propensity and geometry of the nearest neighbor interactions (extended genetic code). The propagation of the interplay of these electrostatic interactions across the hexameric ssDNA chain is considerably less favoured (effectively up to the fourth nucleobase) compared to that of the isosequential ssRNA (up to the sixth nucleobase). The dissection of the relative strength of basepairing and stacking in a duplex shows that stability of DNA-DNA duplex weakens over the corresponding RNA-RNA duplexes with the increasing content of A-T/U base pairs, while the strength of stacking of A-T rich DNA-DNA duplex increases in comparison with A-U rich sequence in RNA-RNA duplexes (Paper X).
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| 7. |
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| 8. |
- Adawi, Tom W., 1970-
(författare)
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From Branes to Brains : On M-theory and Understanding Thermodynamics
- 2002
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis is concerned with research in both physics and physics education, and is divided into two parts.Part IString theory has been the leading candidate over the past few years for a theory that unifies all the fundamental forces of nature. The fundamental objects are one-dimensional strings whose vibrational modes should correspond to the usual elementary particles. However, the recent discovery of the profound role played by extended solitonic objects in string theory, referred to as p-branes, has questioned the foundational position of the string itself. A key ingredient in these developments is the notion of duality, a symmetry which provides a handle on non-perturbative physics. As a result, all five string theories, as well as eleven-dimensional supergravity, are but special limits of a conjectural theory, referred to as M-theory. In this part of the thesis, various aspects of p-branes with relevance for M-theory are investigated. Special emphasis is given to the interpretation of p-branes as solitons. Furthermore, some of the features of the superembedding approach to describe p-brane dynamics are examined.Part IIThere is now a consensus among educational researchers that it is essential to gain a better understanding of how people understand key concepts in physics in order to improve teaching and learning in physics. This part of the thesis reports on a phenomenographic study investigating the qualitatively different ways in which lay adults, taking an introductory overview course in physics, understand the concepts of heat and temperature. Implications for teaching the topics in higher education forms an essential component of the analysis. This is followed by a theoretical component that draws on the empirical analysis as a contribution to the development of the notion of context in phenomenographic research.
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| 9. |
- Adsten, Monika, 1972-
(författare)
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Solar Thermal Collectors at High Latitudes : Design and performance of non-tracking concentrators
- 2002
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Solar thermal collectors at high latitudes have been studied, with emphasis on concentrating collectors. A novel design of concentrating collector, the Maximum Reflector Collector (MaReCo), especially designed for high latitudes, has been investigated optically and thermally. The MaReCo is an asymmetrical compound parabolic concentrator with a bi-facial absorber. The collector can be adapted to various installation conditions, for example stand-alone, roof- or wall mounted. MaReCo prototypes have been built and outdoor-tested. The evaluation showed that all types work as expected and that the highest annually delivered energy output, 340 kWh/m2, is found for the roof MaReCo. A study of the heat-losses from the stand-alone MaReCo lead to the conclusion that teflon transparent insulation should be placed around the absorber, which decreases the U-value by about 30%. A method was developed to theoretically study the projected radiation distribution incident on the MaReCo bi-facial absorber. The study showed that the geometry of the collectors could be improved by slight changes in the acceptance intervals. It also indicated that the MaReCo design concept could be used also at mid-European latitudes if the geometry is changed. A novel method was used to perform outdoor measurements of the distribution of concentrated light on the absorber and then to calculate the annually collected zero-loss energy, Ea,corr, together with the annual optical efficiency factor. A study using this method indicated that the absorber should be mounted along the 20º optical axis instead of along the 65º optical axis, which leads to an increase of about 20% in Ea,corr. The same absorber mounting is suggested from heat loss measurements. The Ea,corr at 20º absorber mounting angle can be increased by 5% if the absorber fin thickness is changed from 0.5 to 1 mm and by 13% if two 71.5 mm wide fins are used instead of one that is 143 mm wide. If the Ea,corr for the standard stand-alone MaReCo with 143 mm wide absorber mounted at 65º is compared to that of a collector with a 71.5 mm wide absorber mounted at 20º, the theoretical increase is 38%.
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| 10. |
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| 11. |
- Ahlsén, Göran
(författare)
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Structure-activity and resistance studies of HIV-1 protease inhibitors
- 2000
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The present investigation was undertaken in order to identify inhibitors of HIV-1 protease that would be efficient in vivo and against HIV-1 protease carrying mutations known to confer resistance to inhibitors in clinical use. A second interest was to understand details of inhibitory mechanisms and to gain understanding of the molecular details of resistance.Linear inhibitors of transition-state type showed to have a resistance pattern similar to protease inhibitors in clinical use, whereas cyclic inhibitors of sulfonamide were somewhat different in their inhibitory profiles. It was found that mutation L90M in some situations could lessen the decrease in overall efficiency suffered by the enzyme when aquiring other mutations. Also presented are results from the characterization of double mutation I84V/L90M, formerly not investigated. Testing of triple and quadruple mutant confirmed the additive features of some mutations. In an attempt to find new leads for inhibitor development, extracts from bee propolis, a natural product, was investigated, and it was found that one extract inhibited wild-type enzyme with an I50-value of 0.2 μg/mL. Even more interesting is the result that propolis extract also inhibited all the investigated mutant enzymes.
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| 12. |
- Akyuz, Mose, 1972-
(författare)
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Positive streamer discharges in air and along insulating surfaces: experiment and simulation
- 2002
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The power quality of modern society relies on the electrical properties of the dielectric insulators used in the power industry. Much research work has been conducted with an aim to understand and predict the insulating behaviour of such materials under different kinds of atmospheric conditions, but still there are many unsolved problems. In particular, there is a lack of knowledge concerning the electrohydrodynamic and electrophysical processes at the insulator surface and the surrounding medium. No detailed knowledge exists at present of the processes governing the development of electrical discharges along the surface of insulators.With an aim to enhance the knowledge in this field in general and on the electrical performance of outdoor insulators in particular a detailed study of the positive streamer discharges in air and along dielectric surfaces was conducted. The study was also extended to gain more knowledge on the water drop initiated electrical discharges in air and the attachment of natural lightning flashes to a Franklin conductor.In the first phase, the study was focused on positive streamer discharges propagating in air. The spatial distribution of the charge of a branched streamer discharge was obtained and the charge contained in a single streamer branch was quantified. In the second phase measurements and simulations of streamer discharges propagating along insulating surfaces were conducted with an aim to understand how the insulating surfaces interact with streamer discharges. In addition to quantifying the parameters of streamer discharges propagating along insulating surfaces, the results of these studies made it possible to separate and quantify the effects of the dielectric constant and the surface properties on the streamer discharges. In the third phase a comprehensive computer algorithm was developed to simulate 3-dimensional propagation of positive streamer discharges in air and along dielectric surfaces taking into account the branching effect. The conditions necessary for the initiation of streamer discharges were applied to obtain the minimum strength of the background electric field required to initiate electrical discharges in the presence of water drops. In particular the study provided an explanation of how lightning flashes are initiated in thunderclouds in background electric fields as low as 200 kV/m. Finally, the study was extended to understand the performance of lightning conductors paying special attention to the influence of conductor radius and the streamer inception criterion.
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| 13. |
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| 14. |
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| 15. |
- Alexander, James N.
(författare)
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Novel detection schemes and high resolution separations in microcolumn liquid separations
- 1999
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Three micro detectors were developed and studied using micro-liquidchromatography (micro-LC). An evaporative light scattering detector (ELSD) nebulizer was developed for use with flow rates ranging from 0.5 to 10 µL/min. The parameters that affect analyte response were investigated and the most influential were capillary tip position and nebulization gas flow rate. One unique advantage of thismicro detector is that it can be operated at ambient conditions which allows for the analysis of semi-volatile compounds.A radio activity monitor (RAM) flow cell was developed for use at 3 µL/min and was designed for coupling to mass spectrometry (MS). The parameters that affect analyte response and band broadening were studied. Reducing the solid scintillant particle size to 9 µm and efficiently packing the solid cells allowed for direct coupling to MS without compromising the chromatographic separation.A nano-electrospray ionization (BSI) source for MS was developed and coupled to nano-LC and capillary electrophoresis (CE). This source incorporated a 50 µm i.d. stainless steel tip that was coupled to the separation capillary. At flow rates of 100 nL/min a stable electrospray was achieved.A multi-use separations system was developed for isocratic and gradient elution micro-LC, capillary electrochromatography (CEC), and pressure CEC (PEC). The details of the system and studies on peak area and retention time repeatability are reported. Comparisons are made between nano-LC and CEC. On average, column efficiency is 57% greater for CEC compared to nano-LC using the same nanocolumn.
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| 16. |
- Alfredsson, Maria
(författare)
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Polar molecules in crystalline and surface environments : From first principles
- 1999
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- With the knowledge of the composition and structure of a chemical system, be it a molecule, a two-dimensional surface or a three-dimensional crystal, it is now possible to predict the specific properties of the compound under consideration via computational studies. Molecular and periodic Hartree-Fock and DFT calculations have been used as a tool to study polar molecules and how their properties respond to the molecular environment in a crystal or on an ionic surface. The investigation covers a range of molecules (HF, HC1, HCN, H2O, OH-, OH., N2, CO and LiF) with different net charges, dipole moments and polarisibility, and a range of crystals and crystalline surfaces: hydrogen-bonded, ionic and ferroelectric.The step-wise build up of the molecular properties (geometries, energies, dipole moments, vibrational frequencies etc.) has been investigated. It was found that sorne molecular properties converge quickly towards the crystal value, others more slowly. Molecules adsorbed on a solid surface were studied as a function of adsorptionenergy, substrate and surface coverage. For the ionic surfaces studied here it was found that the properties of the chemi- and physisorbed molecules are as sensitive to the surface coverage as to the adsorption of the ad-molecule to the surface. The vibrational frequency shift of the ad-molecule has been given special attention.Finally the spontaneous polarisation in two ferroelectric crystals was calculated within the Berry-phase approach.
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| 17. |
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| 18. |
- Alsmark, Cecilia
(författare)
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Comparative Genomics of Obligate and Facultative Intracellular Parasites
- 2002
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The α-proteobacteria Rickettsia prowazekii and Bartonella henselae are the causative agents of epidemic typhus and cat scratch disease respectively. Whereas R. prowazekii is an obligate intracellular parasite, B. henselae can live and proliferate both outside and inside the eukaryotic host cell. Besides the obvious medical interest to identify the complete gene set of two human pathogens, their genome sequences are also important for the study of evolutionary processes. Both R. prowazekii and B. henselae have small genomes, but their last common ancestor of these two bacteria was most likely a free-living organism with a substantially larger genome.The aim of this thesis is to compare the complete genomes of R. prowazekii and B. henselae and to decipher the evolutionary processes leading to the adaptation to an intracellular lifestyle. The working hypothesis was that the facultative intracellular B. henselae is an intermediate between a free living bacteria and the obligate R. prowazekii, which is corroborated. B. henselae has a broader biosynthetic repertoire than R. prowazekii, including the presence of genes for glycolysis and de novo biosynthesis of purines and pyrimidines. However, both bacteria have reduced gene sets for biosynthesis of amino acids and cofactors compared to free-living bacteria.Comparisons of gene order in bacteria reveal that several operons are well conserved between distantly related species. The genome sequences of R. prowazekii and B. henselae show that many of the operons that are usually conserved, are broken and rearranged in these species. One of the mechanisms of reductive evolution include intra-chromosomal recombination between repeated loci. This process expels one of the repeats and cause rearrangements in the gene order of the flanking regions. While the R. prowazekii genome almost completely lack repeated sequences, the B. henselae genome is rich in repeats. These repeats are, however, most often located within regions associated with pathogenicity islands. The higher number of scrambled operons, and the lower number of repeats, in R. prowazekii compared to B. henselae imply that the reductive process has gone further in the former species.
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| 19. |
- Alström, Per
(författare)
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Species Limits and Systematics in Some Passerine Birds
- 2002
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- I use morphological, vocal, molecular, behavioural, ecological and distributional data to re-evaluate the systematics of three passerine bird groups, the Mirafraassamica complex (bush-larks), the genus Seicercus ("spectacled-warblers"; with emphasis on the the S. burkii complex) and the genus Motacilla (wagtails). Two new species are described: Seicercus soror and Motacilla samveasnae. I propose that the polytypic species M. assamica should be treated as four separate species: M. assamica, M. affinis, M. microptera and M. marionae (it is also remarked that the proper name of the latter is M. erythrocephala). That is primarily supported by vocalisations and mitochondrial DNA. The latter data set also suggests that M. assamica sensu lato is paraphyletic, since M. erythroptera, which is always treated as a separate species, is nested within the M. assamica complex. I propose that the polytypic species S. burkii comprises six sibling species. Some of these are found to breed sympatrically, although mainly or entirely segregated altitudinally. Mitochondrial DNA suggests that the S. burkii complex is non-monophyletic, and also that the divergence of the different taxa is much older than indicated by morphological and vocal data. According to the molecular phylogeny, both the genera Seicercus and its assumed sister genus Phylloscopus are paraphyletic. That is corroborated by independent data. The phylogenetic study of the genus Motacilla reveals incongruence between mitochondrial DNA, nuclear DNA and non-molecular data. I conclude that the nuclear gene tree reflects the organismal phylogeny more faithfully than the mitochondrial gene tree. The latter is likely to have been affected by introgressive hybridisation, possibly also stochastic lineage sorting. The most remarkable result that is strongly supported by both mitochondrial and nuclear DNA is that M. flava is non-monophyletic.
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| 20. |
- Amiri, Haleh, 1966-
(författare)
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Patterns and Processes of Molecular Evolution in Rickettsia
- 2002
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Species of the genus Rickettsia are obligate intracellular parasites of the a-proteobacterial subdivision. It has been suggested that obligate intracellular bacteria have evolved from free-living bacteria with much larger genome sizes. Transitions to intracellular growth habitats are normally associated with radical genomic alterations, particularly genome rearrangements and gene losses.This thesis presents a comparative study of evolutionary processes such as gene rearrangements, deletions and duplications in a variety of Rickettsia species. The results show that early intrachromosomal recombination events mediated by duplicated genes and short repeats have resulted in deletions as well as rearrangements. For example, an exceptional organization of the elongation factor genes was found in all species examined, suggesting that this rearrangement event occurred at the early stage of the evolution of Rickettsia. Likewise, it was found that a repetitive element, the so-called Rickettsia Palindromic Element (RPE) flourished prior to species divergence in Rickettsia. Finally, a phylogenetic analysis shows that the duplication events that gave rise to the five genes encoding ATP/ADP transporters occurred long before the divergence of the two major groups of Rickettsia. Taken together, this suggests that Rickettsia have been intracellular parasites for an extensive period of time.A detailed analysis of the patterns of nucleotide changes in genes and intergenic regions among the different species provides evidence for a gradual accumulation of short deletions. This suggests that different distributions of genes and repeated sequences in modern Rickettsia species reflect species-specific differences in rates of deterioration rather than variation in rates of intra-genomic sequence proliferation.
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| 21. |
- Amirkhani, Ardeshir, 1965-
(författare)
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Development of Techniques and Methods for the Quantitative Analysis of Endogenous Substances by Microcolumn Liquid Chromatography Coupled to Mass Spectrometry
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Liquid chromatography-mass spectrometry (LC-MS) is a powerful technique for the analysis of endogenous compounds. The introduction of electrospray ionization (ESI) as an interface between LC and MS has contributed strongly to a trend towards miniaturization of LC, due to the possibility to perform ESI at low flow rates. In this thesis, several aspects regarding the design of miniaturized LC systems and electrospray emitters were investigated. In addition miniaturized LC-ESI-MS have been used for the qualitative and quantitative analysis of endogenous polar compounds, peptides and protein digests.The performance of miniaturized LC-MS was compared using different electrospray emitter configurations. The results indicated that the efficiency of the LC system is rather independent of the configuration of the emitter.The lifetime of gold-coated fused silica electrospray emitters based on vapor deposited adhesion layers of titanium were investigated. The long lifetime of the emitter facilitates the use in LC-MS experiments, exemplified LC-MS by analysis of neuropeptides.The ESI voltage is shown to interfere with liquid chromatographic separations performed in packed porous graphitic carbon capillary column. This interference is ascribed to the presence of an electric field over the conductive column in absence of a ground point between the column and the ESI emitter.The solid supported enhanced microdialysis for analysis of neuropeptides were compared with conventional microdialysis. The difference between the two methodologies were evaluated by LC-MS analysis of the microdialysates. The solid supported method gave in general higher relative recoveries.Finally, a method of standard addition was developed to determine total level of tryptophan and two of its metabolites in human plasma by capillary LC-ESI tandem mass spectrometry. The method was applied in a clinical study of multiple scleroses patients treated with cytokines (IFN Beta 1a, 1b). The results show that the intervention effects the tryptophan metabolism.
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| 22. |
- Andersson, Anna-Carin, 1970-
(författare)
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Postglacial Population History of the Common Shrew (Sorex araneus) in Fennoscandia : Molekylära studier av återkolonisation, könsbundet genflöde och kromosomrasbildning.
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The common shrew, Sorex araneus, has one of the most variable karyotypes among mammals, displaying numerous chromosomes races throughout its distribution, which can be categorized into different karyotypic groups. The objective of this thesis was to examine the postglacial population history of Fennoscandian common shrews using autosomal microsatellites, mitochondrial DNA (mtDNA) and a Y chromosome specific microsatellite (L8Y).Autosomal microsatellites and mtDNA revealed weak genetic structure over a hybrid zone between the karyotypically divergent Northern and Western karyotypic groups. However, the genetic structure displayed by the Y chromosome microsatellite was orders of magnitude higher. Hence, considerable chromosomal differences between the groups do not prevent female gene flow, while male gene flow is reduced (cf. Haldane's rule). Further, the results suggest that the Haldane effect may be caused by the chromosomal differences between the karyotypic groups.No mtDNA differentiation was observed either between chromosome races or between the Northern and Western karyotypic groups in Fennoscandia. The combined pattern of karyotypic and mtDNA variation of Fennoscandian common shrews, suggest bi-directional postglacial recolonisation from a single refugium in Europe. The variation of the Y-linked microsatellite supported this conclusion. In contrast, significant mtDNA structure, discordant with the karyotypic variation, revealed that common shrews in southern Finland belong to a different lineage than remaining Fennoscandian regions, implying postglacial recolonisation from a different source.MtDNA variation of the chromosome races in Sweden supports the hypothesis that three races of the Western karyotypic group have been formed through whole arm reciprocal translocations (WARTs), as suggested by their mutual karyotypic variation. The variation of the molecular markers supports the theory of rapid karyotypic evolution in the common shrew.
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| 23. |
- Andersson, Anna S.
(författare)
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Lithium iron phosphates as cathode materials in lithium batteries
- 2000
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Iron-based oxides are perhaps the only realistic cathode materials for electric and electric-hybrid vehicle applications. Two types of lithium iron phosphate, LiFePO4 andR-Li3Fe2(PO4)3, have been investigated for use within the lithium/lithium-ion polymer batteryconcept. The main techniques exploited have been: electrochemical cycling; X-ray andneutron diffraction - to study structural changes of the host material during lithiuminsertion/extraction; Mössbauer spectroscopy - to probe changes in the local structure of theFe atoms.Lithium extraction/insertion for LiFePO4, (olivine-type structure) has been followed by acombination of in situ X-ray diffraction and in situ Mössbauer spectroscopy. QuantitativeRietveld analysis of diffraction data has given good agreement with electrochemical andMössbauer spectroscopy data: ca. 20% of the LiFePO4 phase remains after charging. Possiblemechanisms to describe the capacity loss are proposed. High-temperature cycling (at 40oC and60oC) has shown the specific capacity to be markedly enhanced at higher temperatures.In situ Mössbauer spectroscopy has also been used to study the insertion of lithium into R-Li3Fe2(PO4)3. The two non-equivalent Fe3+ ions cannot be distinguished, whereas two typesof Fe2+ site appear on lithium insertion. Lithium appears to enter a site closer to one of theFe atoms. Elevated-temperature cycling shows the temperature dependence of R-Li3Fe2(PO4)3to be less marked than for the LiFePO4 system.The magnetic properties of R-Li3Fe2(PO4)3 have been investigated for the first time: a para- to antiferromagnetic transition is seen at 28 ~ K. Neutron powder diffraction shows that the Fe magnetic dipoles lie close to the ab-plane and are ferromagnetically aligned within an Fesheet perpendicular to the c-axis, but are antiferromagnetically coupled to adjacent sheets.
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| 24. |
- Andersson, Anna
(författare)
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Surface Phenomena in Li-Ion Batteries
- 2001
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The formation of surface films on electrodes in contact with non-aqueous electrolytes in lithium-ion batteries has a vital impact on battery performance. A basic understanding of such films is essential to the development of next-generation power sources. The surface chemistry, morphology and thermal stability of two typical anode and cathode materials, graphite and LiNi0.8Co0.2O2, have here been evaluated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction, scanning electron microscopy and differential scanning calorimetry, and placed in relation to the electrochemical performance of the electrodes. Chemical and morphological information on electrochemically formed graphite surface films has been obtained accurately by combining XPS measurements with Ar+ ion etching. An improved picture of the spatial organisation, including thickness determination of the surface film and characterisation of individual component species, has been established by a novel sputtering calibration procedure. The stability of the surface films has been shown to depend strongly on temperature and choice of lithium salt. Decomposition products from elevated-temperature storage in different electrolyte systems were identified and coupled to effects such as capacity loss and increase in electrode resistance. Different decomposition mechanisms are proposed for surface films formed in electrolytes containing LiBF4, LiPF6, LiN(SO2CF3)2 and LiCF3SO3 salts.Surface film formation due to electrolyte decomposition has been confirmed on LiNi0.8Co0.2O2 positive electrodes. An overall surface-layer increase with temperature has been identified and provides an explanation for the impedance increase the material experiences on elevated-temperature storage. Surface phenomena are clearly major factors to consider in selecting materials for practical Li-ion batteries.
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- Andersson, C. Evalena, 1973-
(författare)
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Structure-Function Studies of Enzymes from Ribose Metabolism
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In the pentose phosphate pathway, carbohydrates such as glucose and ribose are degraded with production of reductive power and energy. Another important function is to produce essential pentoses, such as ribose 5-phosphate, which later can be used in biosynthesis of nucleic acids and cofactors. This thesis presents structural and functional studies on three enzymes involved in ribose metabolism in Escherichia coli. Ribokinase is an enzyme that phosphorylates ribose in the presence of ATP and magnesium, as the first step of exogenous ribose metabolism. Two important aspects of ribokinase function, not previously known, have been elucidated. Ribokinase was shown to be activated by monovalent cations, specifically potassium. Structural analysis of the monovalent ion binding site indicates that the ion has a structural rather than catalytic role; a mode of activation involving a conformational change has been suggested. Product inhibition studies suggest that ATP is the first substrate to bind the enzyme. Independent Kd measurements with the ATP analogue AMP-PCP support this. The results presented here will have implications for several enzymes in the protein family to which ribokinase belongs, in particular the medically interesting enzyme adenosine kinase. Ribose 5-phosphate isomerases convert ribose 5-phosphate into ribulose 5-phosphate or vice versa. Structural studies on the two genetically distinct isomerases in E. coli have shown them to be fundamentally different in many aspects, including active site architecture. However, a kinetic study has demonstrated both enzymes to be efficient in terms of catalysis. Sequence searches of completed genomes show ribose 5-phosphate isomerase B to be the sole isomerase in many bacteria, although ribose 5-phosphate isomerase A is a nearly universal enzyme. All genomes contain at least one of the two enzymes. These results confirm that both enzymes must be independently capable of supporting ribose metabolism, a fact that had not previously been established.
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