ABSTRACT
In this study, a novel approach to characterize and identify acidic oil compounds utilizing the fragmentational behavior of their corresponding precursor ions is presented. Precursor ions of seven analyzed pyrolysis oils that were generated from pyrolysis educts of different origins and degrees of coalification were produced by electrospray ionization in the negative ion mode (ESI(-)). Following a fragmentation of all ions in the ion cloud by collision-induced dissociation (CID), the precursor and product ions were subsequently detected by ultrahigh resolving Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The ESI(-)-CID data sets were evaluated by applying either a targeted classification or untargeted clustering approach. In the case of the targeted classification, 10% of the ionized precursor ions of the analyzed pyrolysis liquid samples could be classified into one of 11 compound classes utilizing theoretical fragmentation pathways of these classes. In contrast, theoretical fragmentation pathways were not necessary for the untargeted clustering approach, making it the more transmittable method. Results from both approaches were verified by analyzing standard compounds of known structure. The analysis and data evaluation methods presented in this work can be used to characterize complex organic mixtures, such as pyrolysis oils, and their compounds in-depth on a structural level.
ABSTRACT
Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols.
ABSTRACT
Pyrolysis liquids from coal are complex mixtures of organic compounds with low to high molecular mass and low to high polarity. Compared to low-molecular-weight compounds, little information is available regarding high-molecular-weight compounds in pyrolysis liquids, although their characterization is important for the elucidation of degradation pathways. In this study, laser desorption ionization (LDI) using graphite powder as the support material has been used in conjunction with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) for the analysis of a pyrolysis liquid from brown coal. The acquired data is compared to previous results of the same sample using electrospray ionization (ESI). Using LDI, compounds with masses between 300 and 900 Da were detected by LDI. An evaluation of the spectra was based on the frequency of molecular formulas with a different number of heteroatoms. Hydrocarbon compounds and heteroatomic compounds containing oxygen and sulfur were found. A comparison to ESI results shows that the numbers of observed molecular formulas are virtually the same, but a higher quantity of molecular formulas with a low number of oxygen can be detected by LDI. The observation of molecular formulas without oxygen is a unique feature of the LDI spectra. A more detailed investigation was possible by the utilization of double bond equivalent plots versus carbon number, which revealed a prevalence of LDI for the ionization of compounds with higher DBE.
ABSTRACT
Styrene monooxygenases (SMOs) are flavoenzymes catalyzing the epoxidation of styrene into styrene oxide. SMOs are composed of a monooxygenase (StyA) and a reductase (StyB). The latter delivers reduced FAD to StyA on the expense of NADH. We identified Rhodococcus opacus 1CP as the first microorganism to possess three different StyA isoforms occurring in two systems StyA1/StyA2B and StyA/StyB, respectively. The hydrodynamic properties of StyA isozymes were found to be modulated by the binding of the (reduced) FAD cofactor. StyA1 and SyA2B mainly occur as dimers in their active forms while StyA is a monomer. StyA1 showed the highest epoxidation activity and excellent enantioselectivity in aromatic sulfoxidation. The hydrodynamic and biocatalytic properties of SMOs from strain 1CP are of relevance for investigation of possible industrial applications.
