Normal electrospray ionization Fourier transform ion cyclotron resonance (ESI FT-ICR) mass spectrometry in negative-ion mode has been used to compare the composition of Russian and North Sea crude oils and their eight different distillation fractions (160-210, 210-260, 260-310, 310-360, 360-410, 410-460, 460-510, and 510-560 °C). This is the first time that the polar compound distribution, especially species containing O, O 2 and N atoms, has been studied as a function of temperature. The results obtained are consistent with measured total acid number and nitrogen values; the North Sea crude oil had higher acid but lower nitrogen content compared to the Russian crude oil. The influence of high acid content on the ionization efficiency of other polar species (O and N) in oil samples is also presented for the first time.

Differentiation of beta-amino acid enantiomers with two chiral centres was investigated by kinetic method with trimeric metal-bound complexes. Four enantiomeric pairs of beta-amino acids were studied: cis-(1R,2S)-, cis-(1S,2R)-, trans-(1R,2R)- and trans-(1S,2S)-2-aminocyclopentanecarboxylic acids (cyclopentane beta-amino acids), and cis-(1R,2S)-, cis-(1S,2R)-, trans-(1R,2R)-, and trans-(1S,2S)-2-aminocyclohexanecarboxylic acids (cyclohexane beta-amino acids). The results showed that the choice of metal ion (Cu(2+), Ni(2+)) and chiral reference compound (alpha- and beta-amino acids) had an effect on the enantioselectivity. Especially, aromaticity of the reference compound was noted to enhance the enantioselectivity. The fixed-ligand kinetic method, a modification of the kinetic method, was then applied to the same beta-amino acids, with dipeptides used as fixed ligands. With this method, dipeptide containing an aromatic side chain enhanced the enantioselectivity.

Ion-molecule reactions of protonated cavitands with neutral amines have been studied using electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. The cavitands studied are built by bridging a resorcin[4]arene skeleton with four aryl phosphate units. Each of the PdO bonds can be directed toward the inside or the outside of the cavity leading to six stable diastereoisomers. ESI proved to be an effective ionization method for the cavitands, although the range of ionic species observed strongly depended on the orientation of the PdO groups in the isomers and the solvent composition used. Five protonated diastereoisomers were studied in ion-molecule reactions with various types of neutral amines, and the corresponding reaction efficiencies were calculated. The data were compared with that observed for the complexes generated in solution. Collision-induced dissociation (CID) was used to study the structure and relative stability of the complexes formed from different diastereomers both in solution and in the gas phase. The results clearly show that inclusion complexes are formed in the gas phase, but only for some isomers. Although all of the protonated diastereoisomers reacted with amines, the reaction rates were much lower for the diastereoisomers known to form inclusion complexes in solution. When a proton bound dimer was formed, which had the hydrogen bonding established outside the cavity, the reaction took place at the collision rate. Also, CID results confirmed the inclusion complex formation. The cavitand isomers, carrying two or more coordinating PdO groups oriented toward the inside of the cavity, proved to be strong ligands for the charged species, including the proton, organic ammonium ions, and even alkali metal cations, with cesium showing the highest affinity.

Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry was used for compositional analysis of polar and asphaltene fractions of complex oil residues. The samples were collected before and after the processing of oil in a residue hydrocracking unit, in which the feed oil was the vacuum distillation residue of the crude oil, and the product sample was the residue collected after the processing. From the asphaltene fraction, as many as ∼26 000 peaks were detected by atmospheric pressure photoionization and more than ∼33 000 peaks by positive-ion electrospray ionization (ESI), with up to 18 distinct heteroatom classes identified. Negative-ion ESI provided complementary information through selective ionization of acidic compounds. The detected species were sorted based on heteroatom class, carbon number and aromaticity (double bond equivalence, i.e. number of rings + double bonds to carbon). The N 1 class compounds were predominant in both fractions of the feed and product oils. The sulfur-containing compounds were mainly degraded or removed during the processing as expected. Vanadyl porphyrins (heteroatom class N 4 O 1 V 1 ), detected in the asphaltene fraction of the feed oil, were not observed in the product oil fractions that is consistent with their efficient removal. Increase in the aromaticity for the most heteroatom classes was generally noticed in both polar and asphaltene fractions.

This paper discusses an FT-ICR mass spectrometry study of Russian and North Sea crude oils and their six distillation fractions (260–310, 310–360, 360–410, 410–460, 460–510, and 510–560 °C) by positive electrospray ionization (ESI) mode. Only one major heteroatom class, N class (pyridine benzologues), was found for both crude oils and for every distillation fraction. The relative abundance of N class was found to be somewhat higher for North Sea oil than the Russian oil, containing higher series (DBE values) and carbon distributions. On the other hand, the second most abundant class found for crude oils, the NS class, was found to be more abundant for Russian than North Sea oil samples, in accordance with experimentally measured sulfur values for crude oils. Correspondingly, Russian oil contained a higher series and also carbon distributions NS compounds, in comparison to North Sea oil. The oxygen containing sulfur compounds (OS class) were present only at a low distillation temperature (<410 °C) fractions. The results show that compounds present at trace amounts are more easily observed from distillation fractions than in crude oils.