The detection of enantiomeric purity is an important part of synthetic chemistry. Especially when developing medicinal compounds the determination of the amount of enantiomeric impurities is important as one of the enantiomers may be poisonous or lethal to humans. Various methods exist for the study of enantiomeric purity and NMR spectroscopy has been intensively studied as a tool for this purpose. As NMR is fast, readily available and easy to use it provides an attractive way to study enantomeric purity. In NMR chiral discrimination is obtained by using chiral derivatising agents (CDAs) or chiral solvating agents (CSAs). CSAs have more potential in enantiomeric excess (ee) studies than CDAs as they lack of the disadvantaged of CDAs (e.g. kinetic resolution and racemisation). As chiral carboxylic acids are important in the synthesis of medicinally attractive compounds, natural products and their metabolites, CSAs which can be used for the determination of enantiomeric purity of carboxylic acids and are easily available and cheap are helpful. The present study mainly focuses on the development of CSAs suitable for the discrimination of non-ionic and ionic chiral carboxylic acids. (+)-Dehydroabietylamine was used as chiral building block for these new CSAs as it has several beneficial features such as easy availability, low price, an amenable structure for CSA construction and it is known to resolve chiral carboxylic acids via cystallisation. Three different series of non-ionic and ionic CSAs were developed from (+)-dehydroabietylamine: 1) ammonium, 2) secondary amine and 3) imidazolium based CSAs. Their enantiomeric discrimination abilities were examined with Mosher s acid and its tetrabutylammonium salt. Best resolution was obtained with non-ionic substrate and non-ionic CSA and with ionic substrate and ionic CSA. Ionic CSAs were also able to resolve non-ionic substrates but the enantiomeric resolution remained poor. The best performing CSAs were subjected for more detailed investigation. The stoichiometry of formed diastereomeric complex between the CSA and substrate was studied by titration experiment. CSA-substrate complexes were generally formed in 1:1 ratio. CSA applicability to function in ee determination was studied and they were able to detect the enantiomeric purities of samples with excellent reliability. Finally their ability to resolve various α-substituted carboxylic acids was studied showing that (+)-dehydroabietylamine based CSAs are suitable for chiral carboxylic acids containing electronegative α-substituent. Also the effect of measurement conditions and sample preparation when using cationic CSAs in enantiomeric discrimination was investigated. Lower temperatures and low polarity solvents were noticed to increase enantiomeric discrimination, among high CSA concentration. Delocalisation of negative charge in counter anion of CSA as well as the use of organic counter cation for the substrate was also notised to increase enantiomeric discrimination.

Sulfuric and hydrochloric acids participate in several important chemical processes occurring in the atmosphere. Due to its tendency to react with water molecules, sulfuric acid is an important factor in cloud formation and related phenomena. Hydrochloric acid is heavily implicated in stratospheric ozone depletion because of its role as a temporary reservoir for chlorine radicals. In this thesis, the thermodynamics and dynamics of these two acids are investigated. The dynamic part focuses on the chemical processes following collision of HCl on water and amorphous ice surfaces at different temperatures. By utilizing ab initio molecular dynamics, it is observed that the surface temperature and the initial kinetic energy of the HCl molecule have important and not wholly overlapping effects on its ionization behaviour. The results add to the understanding of hydrochloric acid dissociation on water surfaces in various parts of the atmosphere, potentially illuminating new pathways for related chemical reactions, such as the formation of ClNO on amorphous ice surfaces. The thermodynamic studies revolve around the impact of multiple low-lying stable conformers, or global anharmonicity, on the thermodynamic properties. The studies for this part focus on complexes of sulfuric acid, especially sulfuric acid monohydrate. Due to the relatively small size of the monohydrate, high-level ab initio methods can be employed to obtain accurate values for its thermodynamic properties, thus providing a reliable basis for comparison with less accurate approaches. New ways of accounting for global anharmonicity are developed both for small- and medium-sized clusters. For small clusters, an approximation is presented where the large amplitude motions connecting different conformers are treated separately from the rest of the vibrations, resulting in direct quantum mechanical accounting of the different conformers. In the case of medium-sized clusters, an equation based on statistical mechanics is derived to replace the erroneous Boltzmann averaging formula that has seen wide use in the literature.

This thesis covers two aspects of utilisation of advanced separation technology together with mass spectrometry: 1. Drift tube ion mobility spectrometry mass spectrometry (IMS-MS) studies of the behaviour of ions in the gas phase and 2. Comprehensive two dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOF-MS) studies for characterization of crude oil samples. In IMS studies, the focus was on the separation of isomeric compounds. For example, [M-H]- ions of 2,4-di-tert-butylphenol (2,4-DtBPh) and 2,6-di-tert-butylphenol (2,6-DtBPh) were separated. It was also observed that shielding of the charge site by the functional groups of a molecule has a large effect on the separation of the isomeric compounds. For example, amines with a shielded charge site were separated from those with a more open charge site, while some of the isomeric amines studied were not separated. Different kinds of adduct ions were observed for some of the analytes. Dioxygen adducts were seen for 2,4-DtBPh [M+O2]-, 2,6-di-tert-butylpyridine (2,6-DtBPyr) [M+O2]+· and 2,6-di-tert-butyl-4-methylpyridine (2,6-DtB-4MPyr) [M+O2]+·. The adduct formation increases the total mass of the analyte ion, and therefore, for example the 2,4-DtBPh [M+O2]- ion could be separated from its isomeric compound 2,6-DtBPh [M-H]-, which did not from the dioxygen adduct ion. In the case of 2,6-DtBPyr and 2,6-DtB-4MPyr, the [M]+ ions formed dioxygen adduct [M+O2]+· ions. The both ions, [M]+ and [M+O2]+·, shared the same drift time which was longer than their [M+H]+ ion species. This work demonstrates that measuring with IMS the mobility of different ion structures of the same molecule, especially dioxygen adducts, results in a better understanding of the role of adduct ions in the IMS-separation process. In GC×GC-TOF-MS studies, the focus was on detailed characterization of crude oil samples. For instance, oils from the Recôncavo Basin were classified to two different groups by using minor oil components. The GC×GC-TOF-MS data showed the correlation between 2D retention time and the number of carbons in a ring for several hydrocarbons as known from the literature. This information was used to achieve more structural information about eight new tetracyclic compounds, some of them similar to nor-steranes, detected during analysis. Some of these new compounds could be used as maturity indicators. This study demonstrated how GC×GC-TOF-MS can be used to separate geochemically interested isomers, identify minor geochemical differences between oils and achieve structural information about unknown biomarkers.

There is nowadays a strong concern about decreasing oil supplies and global warming leading to ever increasing interest in biobased fuels and chemical production. The utilization of lignocellulosic raw materials for liquid biofuels and chemicals is a challenging task due to raw materials rigid structure which is resistant towards any actions to break it. Thus the raw materials should be pretreated to reach an economically vital process. Catalytic and alkaline oxidation presented here are novel, highly selective and effective methods to separate carbohydrates from lignin in different lignocellulosic materials. Both pretreatment methods are carried out at 120 140 ˚C for 4 20 hours under 10 bar oxygen pressure and in alkaline water solution. In catalytic oxidation also copper(II) phenanthroline catalyst is used. The obtained carbohydrate rich fraction is remarkably easy to hydrolyze with enzymes to corresponding sugars. The carbohydrate rich material from catalytic oxidation is nearly quantitatively converted into corresponding monohydrates in 24 hours by enzymatic hydrolysis. The enzyme loading can also be significantly decreased compared to standard methods, which helps to decrease the total costs of the process. Catalytic and alkaline oxidation pretreatment methods can be applied also to chromated copper arsenite treated waste wood, which is considered as hazardous waste. When combined with very mild sulfuric acid extraction and enzymatic hydrolysis 90 % sugar yield is obtained from the carbohydrate material. The sugars can be further utilized in chemical industry, which makes this method an interesting way to recycle hazardous waste. In a process turning lignocellulosic materials into sugars hydrolysis plays the key role. The hydrolysis is usually carried out enzymatically or with acids. They both have their disadvantages, such as long reaction times, poor yields or corrosive effect. As an alternative to traditional acid hydrolysis a microwave assisted mild acid hydrolysis is presented here. It can be applied to xylan, which is converted to xylose quantitatively in just one minute with 2 wt-% hydrochloric acid. When applied to milled birch wood 70 % yield of xylose is obtained. Subjecting alkaline oxidation pretreated birch to a three-step reaction, all the xylan and 66 % of the cellulose is hydrolyzed to corresponding sugars.

Despite the similarity of their structural basic units, cellulose- and starch-based materials behave differently in many industrial applications. In this thesis, the structure and properties of these polysaccharides and their selected derivatives were studied by means of five comprehensive examples. In the first investigation, highly crystalline cellulose was identified from Valonia macrophysa vesicles by atomic force microscopy. The role of water as a possible modifier on the surface of cellulose was found to be very important. The monoclinic phases were found on the cellulose surfaces with a lateral resolution of about 4 Å, indicating that water molecules cannot penetrate and thus disturb the surface structure of monoclinic cellulose. On the other hand, the absence of triclinic phases was explained by the used measuring geometry without liquid cell. The ageing of metastable oat and barley thermoplastic starch films was followed by frictional imaging. As a consequence of the ageing, the films lose some of their mechanical properties. In the oat films, glycerol used as a plasticiser diffused from the starch-glycerol-water matrix to the surface of thermoplastic starch, resulting in areas with low friction. In the case of barley starch films, the ageing first resulted in short range reorientation of polymers and finally slow crystallization of amylopectin branches. Solution precipitation techniques were applied to produce ideally spherical starch ester particles (with a diameter about half the wavelength of visible light), suitable for fillers in paper coatings in the third study. Particles assume their shape and size spontaneously when solvated starch polymer is mixed with non-solvent, due to the free mobility of the modified starch chains. Starch pigment has improved affinity to paper surface and it can be used as such or mixed with other pigments to enhance the optical or printing properties of paper. Starch-based pigmenting materials with improved optical performance were prepared in the laboratory by the complexation approach. Analytical results indicated that the complexation of carboxymethyl starch and inorganics strongly depends on the carboxymethyl group in the starch-based hybrid pigmented materials. The formed insoluble hybrids were mostly amorphous and the crystalline contribution of the inorganic component was not evident. The resulting precipitates exhibited composite structures. Finally, three starch-based and two cellulose-based polymers were selected for flocculation and filtration tests. In shearless dewatering conditions, the retention and dewatering properties of the starch-based polymers were similar to those of commercial polyacrylamide-based polymers. The flow studies in higher shear conditions showed that with the studied dosages the starch-based polymers could not reach the flocculation levels needed to maintain sufficient retention properties. The performance of the cellulose-based polymers as flocculating agents was less efficient. The reasons for the more limited performance of the polysaccharide-based flocculants were too low molecular weight and the charge density distribution. Better understanding of how to improve the hydrodynamic properties of bio-based polymers will be essential when planning new bio-based flocculants. The deeper understanding of the relationships between the desired structures and properties of polysaccharides helps to utilize them more effectively. In this way it is possible to obtain better bio-based and environmentally sustainable products in the competition with the current products based on conventional petrochemistry.

Theoretical examination of traditional nuclear magnetic resonance (NMR) parameters as well as novel quantities related to magneto-optic phenomena is carried out in this thesis for a collection of organic molecules. Electronic structure methods are employed, and reliable calculations involving large molecules and computationally demanding properties are made feasible through the use of completeness-optimized basis sets. In addition to introducing the foundations of NMR, a theory for the nuclear spin-induced optical rotation (NSOR) is formulated. In the NSOR, the plane of polarization of linearly polarized light is rotated by spin-polarized nuclei in an NMR sample as predicted by the Faraday effect. It has been hypothesized that this could be an advantageous alternative to traditional NMR detection. The opposite phenomenon, i.e., the laser-induced NMR splitting, is also investigated. Computational methods are discussed, including the method of completeness optimization. Nuclear shielding and spin-spin coupling are evaluated for hydrocarbon systems that simulate graphene nanoflakes, while the laser-induced NMR splitting is studied for hydrocarbons of increasing size in order to find molecules that may potentially interest the experimentalist. The NSOR is calculated for small organic systems with inequivalent nuclei to prove the existence of an optical chemical shift. The existence of the optical shift is verified in a combined experimental and computational study. Finally, relativistic effects on the size of the optical rotation are evaluated for xenon, and they are found to be significant. Completeness-optimized basis sets are used in all cases, and extensive analysis regarding the accuracy of results is made.

The chemical and physical properties of bimetallic clusters have attracted considerable attention due to the potential technological applications of mixed-metal systems. It is of fundamental interests to study clusters because they are the link between atomic surface and bulk properties. More information of metal-metal bond in small clusters can be hence released. The studies in my thesis mainly focus on the two different kinds of bimetallic clusters: the clusters consisting of extraordinary shaped all metal four-membered rings and a series of sodium auride clusters. As described in most general organic chemistry books nowadays, a group of compounds are classified as aromatic compounds because of their remarkable stabilities, particular geometrical and energetic properties and so on. The notation of aromaticity is essentially qualitative. More recently, the connection has been made between aromaticity and energetic and magnetic properties. Also, the discussions of the aromatic nature of molecular rings are no longer limited to organic compounds obeying the Hückel’s rule. In our research, we mainly applied the GIMIC method to several bimetallic clusters at the CCSD level, and compared the results with those obtained by using chemical shift based methods. The magnetically induced ring currents can be generated easily by employing GIMIC method, and the nature of aromaticity for each system can be therefore clarified. We performed intensive quantum chemical calculations to explore the characters of the anionic sodium auride clusters and the corresponding neutral clusters since it has been fascinating in investigating molecules with gold atom involved due to its distinctive physical and chemical properties. As small gold clusters, the sodium auride clusters seem to form planar structures. With the addition of a negative charge, the gold atom in anionic clusters prefers to carry the charge and orients itself away from other gold atoms. As a result, the energetically lowest isomer for an anionic cluster is distinguished from the one for the corresponding neutral cluster. Mostly importantly, we presented a comprehensive strategy of ab initio applications to computationally implement the experimental photoelectron spectra.

The oxidation of alcohols to the corresponding carbonyl compounds is a key reaction in the synthesis of organic chemicals. Consequently, a vast number of diverse methods based on copper that accomplish this functional group transformation are reviewed in this work. A successful development from pressurized oxygen to open air and from organic to environmentally friendly water solvent in oxidation of alcohols to the corresponding carbonyl compounds catalyzed by copper is presented. The first direct organocatalytic oxidation of alcohols to aldehydes with O2 in alkaline water was developed. One of the effects metal ions on the reaction was that the Cu ion is the most beneficial recipient of quantitative oxidation. Thus aerobic oxidation of alcohols to the corresponding carbonyl compounds catalyzed by TEMPO/Cu 2 N arylpyrrolecarbaldimine in alkaline water was discovered. The solid and solution structures of sterically hindered salicylaldimine and cis trans isomers of the corresponding Cu(II) complexes are discussed. High yield synthetic routes for mixed ligand Cu(II) complexes derived from salicylaldehyde and the corresponding salicylaldimine were developed. New crystal structures of the above compounds were determined by X ray crystallography. The catalytic property of homo and heteroligated bis(phenoxidoyimino)Cu(II)complexes toward oxidation reactions were investigated. Accordingly, facile base free aerobic oxidations of alcohols to aldehydes and ketones in toluene using low loading of both TEMPO and catalysts under mild conditions were introduced. In addition to the aerobic catalytic methods, oxidation of alcohols to the corresponding carbonyl compounds with H2O2 as an end oxidant in pure water using simple CuSO4 as a catalyst is presented. The effect of various additives, such as acids or bases, radical scavengers and N containing ligands, on the efficiency/selectivity of the catalyst system was studied as well. Finally, highly efficient open air oxidation of alcohols in water catalyzed by in situ made Cu(II) phenoxyimine complexes without additional auxiliarities such as base or co solvent are described.