Polymer electrolytes are an essential part of the modern all-solid lithium battery. Several properties, such as mechanical and thermal stability, good ionic conductivity and compatibility with other materials used in the battery are necessary for a successful material.

This thesis is focused on the ionic interactions in two electrolyte systems, based on a cross-linked polyethylene oxide (nona(ethylene oxide)dimethacrylate) or a fluorinated copolymer (polyvinylidene fluoride-hexafluoropropylene). Changes of thermal properties and morphology of and coordination in the electrolyte on addition of a lithium salt (LiTFSI) and different types and concentrations of solvents are studied. These properties are shown to control the ionic conductivity of the resulting material, influencing the conductivity mechanism.

The presumably inert polyvinylidene fluoride is shown to undergo large structural changes, where polar conformations of the polymer backbone appear on salt addition, inducing a different crystalline phase. The lithium cation in the polyethylene oxide based electrolyte can coordinate either to the polymer chain or to the solvent. In for example systems containing propylene carbonate, the lithium ion binds more strongly to the polymer than to the solvent. This is in contrast to the systems with dimethyl sulphoxide where the ion prefers the solvent. This variation in coordination also strongly affects the mobility of the cation, reflected both in diffusion constants and in conductivity data.

A combination of techniques was necessary to use for a deeper understanding of these complex materials. Coordination has been studied by FTIR and high resolution NMR, dynamics by NMR diffusion measurements and impedance spectroscopy, and morphology by diffraction techniques and DSC.

The influence of two plasticizers, propylene carbonate and dimethyl sulphoxide, as well as different salt concentrations of Li(TFSI), on properties of a polymer gel electrolyte material has been studied using differential scanning calorimetry (DSC) and ac impedance and FTIR spectroscopy. Variations of glass transition temperature and the conductivity behaviours of the systems were examined, and found to be highly dependent on the amount and type of the plasticizer used. Characteristic band-shifts in FTIR spectra, indicating coordination of lithium ions, have been found for the polymer and both the plasticizers in the corresponding binary solutions. These shifts were used to study the coordination preferences in the complete ternary electrolyte system. The combined results from the three experimental techniques have been discussed.

The base-catalysed 1,3-proton transfer reactions in 1-methylindene have been studied theoretically in polar (water) and unpolar (cyclohexane) solvents, respectively, for two different choices of bases, namely ammonia and trimethylamine (TMA), using the SM

Being a major cause of eutrophication and subsequent loss of water quality, the turnover of phosphorus (P) in lake sediments is in need of deeper understanding. A major part of the flux of P to eutrophic lake sediments is organically bound or of biogenic origin. This P is incorporated in a poorly described mixture of autochthonous and allochthonous sediment and forms the primary storage of P available for recycling to the water column, thus regulating lake trophic status. To identify and quantify biogenic sediment P and assess its lability, we analyzed sediment cores from Lake Erken, Sweden, using traditional P fractionation, and in parallel, NaOH extracts were analyzed using 31P NMR. The surface sediments contain orthophosphates (ortho-P) and pyrophosphates (pyro-P), as well as phosphate mono- and diesters. The first group of compounds to disappear with increased sediment depth is pyrophosphate, followed by a steady decline of the different ester compounds. Estimated half-life times of these compound groups are about 10 yr for pyrophosphate and 2 decades for mono- and diesters. Probably, these compounds will be mineralized to ortho-P and is thus potentially available for recycling to the water column, supporting further growth of phytoplankton. In conclusion, 31P NMR is a useful tool to asses the bioavailability of certain P compound groups, and the combination with traditional fractionation techniques makes quantification possible.

This contribution describes how de novo designed synthetic helix–loop–helix polypeptides are utilized tocontrol the assembly of gold nanoparticles and as scaffolds for biosensing. The synthetic polypeptides aredesigned to fold into a four-helix bundle upon dimerization. When immobilized on gold nanoparticles,dimerization and folding occur between peptides on neighbouring particles as an effect of particleaggregation and the folded polypeptides are rigid enough to keep the particles separated at a distancecorresponding to the size of the four-helix bundle. Moreover, peptide dimerization offers a convenientroute to assemble nanoparticles into hybrid multilayers on planar substrates. The drastic change in theresonance conditions of the localized nanoparticle surface plasmon upon particle aggregation is shown tobe useful for optical detection of biomolecular interactions.

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.

An automated liquid nano-separation system has been developed for nano-liquid chromatography (nano-LC) and capillary electrochromatography (CEC) using both isocratic and gradient elution, One fused-silica nanocolumn, typically 75 mu m i x 39 cm (25 cm ef

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.

Treatment of 1-(benzylselenenyl)-5-butyl-5-nonanoI (10) with oxalyl chloride followed by the sodium salt of N-hydroxypyridine-2-thione afforded the corresponding pyridine-2-thione-N-oxycarbonyI (PTOC) oxalate ester which was not isolated but immediately h

A highly diastereoselective reaction of 2-azanorbornyl enolates with electrophiles has been studied. Deprotonation of 4 with LDA at low temperature affords the corresponding exocyclic lithium enolate 5, which reacts with different electrophiles such as al

2-Azanorbornyl-derived amino alcohols were prepared and evaluated as ligands in the Ru(II)-catalyzed asymmetric transfer hydrogenation of aromatic ketones. To improve selectivity and rate, the structure of the ligand was optimized, Acetophenone was reduce

The mechanism of the Ru(arene)(amino alcohol)-catalyzed transfer hydrogenation of ketones using isopropyl alcohol as the hydrogen source has been studied by means of hybrid density functional methods (B3PW91). Three mechanistic alternatives were evaluated, and it was shown that the reaction takes place via a six-membered transition state, where a metal-bound hydride and a proton of a coordinated amine are transferred simultaneously to the ketone. Further calculations provided a general rationale for the rate of the reaction by comparison of steric effects in the ground and transition states of the ruthenium hydride complex. It was found that the TS has a strong preference for planarity, and this in turn is dependent on the conformational behavior of the O,N-linkage of the amino alcohol ligand. Finally, a general model, rationalizing the enantioselectivity of the reaction, was developed. Experimental studies of both rate and enantioselectivity were used in order to support the computational results.

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.

Tryptophan and its metabolites are of great interest in understanding the pathogenesis of multiple sclerosis (MS). The total levels of tryptophan and its metabolites, kynurenine and kynurenic acid were determined in plasma by capillary liquid chromatography electrospray ionisation tandem mass spectrometry. This is the first report of the plasma levels of these analytes in healthy controls and relapsing-remitting MS patients receiving long-term and acute interferon-beta (IFN-beta) treatment. Twenty-four hours post-administration increased kynurenine levels (first IFN MS versus healthy, P = 0.042) and kynurenine/tryptophan ratio (K/T; first IFN MS versus healthy, P =0.027; first IFN MS versus long-term IFN MS, P = 0.036) were found. The long-term IFN MS group had higher K/T ratios at 4 and 12 h post-administration (P = 0.015 and 0.009, respectively). The increase of K/T ratio in the first IFN MS group indicate an induction of the enzyme indolamine-2,3-dioxygenase (IDO), as reported earlier in experimental allergic encephalomyelitis. As IDO is participating in both inflammatory and neurodegenerative processes, further knowledge of its involvement in the pathogenesis of MS is of great importance.

Four different sheathless electrospray ionization (ESI) configurations were investigated for a nano liquid chromatography (LC) system. The studied configurations were: a column with an integrated emitter, with the ESI potential applied before or after the column, and a column with separate emitter, with the ESI voltage applied at a union before the emitter or at the emitter tip. The results indicates that the efficiency of the LC system is rather independent of the configuration when using 95 μm i.d. columns, acetic mobile phase and standard peptides as a sample. Introduction of post column dead volume seems not to be a critical issue at least with flow rates down to 600 nl/min.

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 40^oC and60^oC) 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.

Magnetic susceptibility measurements indicate that rhombohedral Li3Fe2(PO4)(3), obtained by ion exchange of monoclinic Na3Fe2(PO4)(3), exhibits a paramagnetic to antiferromagnetic transition at T-N approximate to 27 K. Curie-Weiss-like behaviour is observ

The capacity and cyclability of solid-state synthesized LiFePO4-based laminate cells of type <Li \ liq. el. \ LiFePO4> have been studied at 23, 40, and 60 degrees C. Larger capacities were obtained for cells cycled at the elevated temperatures. No evidenc

A modified standard addition method for single element determination by X-ray fluorescence spectrometry has been studied. The attenuation properties of the standard added samples are kept constant by adding decreasing amounts of an attenuation modifier along with increasing amounts of a standard. In this way the standard addition curve will be a straight line in cases where the ordinary standard addition curve is non-linear, and linear regression can be used to evaluate the concentration of the analyte. Standard additions of oxides of a number of elements, with and without modifier, have been made to cellulose powder or a mixture of aluminium oxide and polyethylene as matrices in order to test the method. The method has been applied to the determination of zinc in fly-ash from a steel work and of iron in cement. The fly-ash contained about 5% of zinc and the cement samples between 2 and 5% of Fe(2)O(3). The results were compared with those obtained by ICP-AES after decomposition of samples in lithium tetraborate or lithium metaborate and dissolution of the melt in 10%(v/v) nitric acid. The results agreed within 2%, relative, for fly-ash and within 3-6%, relative, for cement samples.

Lead in fly-ash from a garbage incinerator has been determined by X-ray fluorescence spectrometry (XRFS) and a modified standard-addition method. To keep the attenuation properties of the spiked samples constant, decreasing amounts of an attenuation modifier [mercury (II) acetate] were added together with increasing amounts of the standard (lead nitrate). Linearity between fluorescence intensity and amount of lead was thus obtained, so the amount of lead in the sample could be evaluated by linear regression. The amount of modifier needed could be calculated from a simple expression. The method was validated by comparison with the results obtained by applying atomic-absorption spectrometry (AAS) to solutions made by leaching the fly-ash with strong acid. For 8 fly-ash samples, containing between 0.8 and 1.35% lead, the largest absolute difference between the two sets of results was 0.03%. Theoretical calculations based on a simplified version of the Sherman equation were performed to confirm the linearity of the modified standard-addition curves.