Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures – Application to the petroleomic analysis of bio-oils

Abstract

The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to CHO with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture.

Studying the fragmentation mechanism of selected components present in crude oil by collision‐induced dissociation mass spectrometry

“…For a better understanding of such materials, analytical chemistry plays an important role. Ultrahigh-resolution mass spectrometry, due to its unmatched resolving power and high mass accuracy, has developed into the method of choice for their analysis [1][2][3][4][5][6][7][8][9] and allows a more detailed understanding of the extremely complex mixture, called a supercomplex mixture, 8 that makes up a crude oil. 10,11 Still, there are some issues where even mass spectrometric methods show shortcomings.…”

Study of the mainstream cigarette smoke aerosols by Fourier transform ion cyclotron resonance mass spectrometry coupled to laser/desorption and electrospray ionization – Additional insights on the heteroaromatic components

“…The amount of oxygen in the final products is consequently higher than what is observed with “normal cigarettes” and favors the formation of oxygenated MSS compounds. As the composition of the biomass content of the cigarette is different, the investigation of MSS by LDI and ESI FTICR‐MS in negative detection mode may give relevant information as we demonstrated on the study of bio‐oil generated from biomass pyrolysis . The investigation of Indonesian and Kretek MSS by (−) LDI gives additional insights into the contribution of cloves to the final products observed in the MSS particle phases.…”

“…Compounds with up to eight oxygen atoms are observed and the center of the Gaussian distribution is shifted to O5–O6 species. Such C x H y O w distributions have still been evidenced in the study of bio‐oil produced by pyrolysis of lignin or biomass and are relevant to the thermal degradation of the lignin, cellulose and hemicellulose of the biomass . The C x H y O w species observed in the study of Kretek MSS correspond to the superposition of the pyrolysis products of tobacco (O2 to O5), which typically contains 10% of cellulose, 12.5% of sugars and 3.5% of lignin and the pyrolysis of the cloves (O4 to O8), which is a ligno‐cellulosic material and contains close to 60% of cellulose and sugar .…”

“…They are from the combustion/pyrolysis of the lignocellulosic part of tobacco. Indeed, such species have been also observed when the products of the pyrolysis of lignocellulolisic material are investigated . Whatever the ionization technique, the observation of C x H y O w − or C x H y N z O w − species is favored by the ability of deprotonated hydroxyl groups associated with phenols or derivatives of benzoic acids to be stabilized by resonance phenomena, involving more than one aromatic ring.…”

“…The increase in the laser fluence generally leads to a recombination phenomenon which may be associated with the clustering phenomenon . To increase the knowledge of the composition of the cigarette smoke particle fraction, electrospray ionization (ESI) may be regarded as a complementary ionization technique as recently demonstrated for bio‐oil analysis . Indeed, the ability of ESI to efficiently ionize polar compounds, which are poorly detected by LDI, may be helpful to obtain a more complete description of such complex samples.…”