5 research outputs found
Hyphenation of Thermal Analysis to Ultrahigh-Resolution Mass Spectrometry (Fourier Transform Ion Cyclotron Resonance Mass Spectrometry) Using Atmospheric Pressure Chemical Ionization For Studying Composition and Thermal Degradation of Complex Materials
In this study, the hyphenation of
a thermobalance to an ultrahigh-resolution
Fourier transform ion cyclotron resonance mass spectrometer (UHR FTICR
MS) is presented. Atmospheric pressure chemical ionization (APCI)
is used for efficient ionization. The evolved gas analysis (EGA),
using high-resolution mass spectrometry allows the time-resolved molecular
characterization of thermally induced processes in complex materials
or mixtures, such as biomass or crude oil. The most crucial part of
the setup is the hyphenation between the thermobalance and the APCI
source. Evolved gases are forced to enter the atmospheric pressure
ionization interface of the MS by applying a slight overpressure at
the thermobalance side of the hyphenation. Using the FTICR exact mass
data, detailed chemical information is gained by calculation of elemental
compositions from the organic species, enabling a time and temperature
resolved, highly selective detection of the evolved species. An additional
selectivity is gained by the APCI ionization, which is particularly
sensitive toward polar compounds. This selectivity on the one hand
misses bulk components of petroleum samples such as alkanes and does
not deliver a comprehensive view but on the other hand focuses particularly
on typical evolved components from biomass samples. As proof of principle,
the thermal behavior of different fossil fuels: heavy fuel oil, light
fuel oil, and a crude oil, and different lignocellulosic biomass,
namely, beech, birch, spruce, ash, oak, and pine as well as commercial
available softwood and birch-bark pellets were investigated. The results
clearly show the capability to distinguish between certain wood types
through their molecular patterns and compound classes. Additionally,
typical literature known pyrolysis biomass marker were confirmed by
their elemental composition, such as coniferyl aldehyde (C<sub>10</sub>H<sub>10</sub>O<sub>3</sub>), sinapyl aldehyde (C<sub>11</sub>H<sub>12</sub>O<sub>4</sub>), retene (C<sub>18</sub>H<sub>18</sub>), and
abietic acid (C<sub>20</sub>H<sub>30</sub>O<sub>2</sub>)
Experimental set-up and global omics analyses.
<p>(A) An 80 KW common-rail-ship diesel engine was operated with heavy fuel oil (HFO) or refined diesel fuel (DF). The exhaust aerosols were diluted and cooled with clean air. On-line real-time mass spectrometry, particle-sizing, sensor IR-spectrometry and other techniques were used to characterise the chemical composition and physical properties of the particles and gas phase. Filter sampling of the particulate matter (PM) was performed to further characterise the PM composition. Lung cells were synchronously exposed at the air-liquid-interface (ALI) to aerosol or particle-filtered aerosol as a reference. The cellular responses were characterised in triplicate at the transcriptome (BEAS-2B), proteome and metabolome (A549) levels with stable isotope labelling (SILAC and <sup>13</sup>C<sub>6</sub>-glucose). (B) Heatmap showing the global regulation of the transcriptome, proteome and metabolome.</p
Summary of the main HFO- and DF-particle exposure effects.
<p>The arrows indicate the direction of regulation for cellular functions derived from the most statistically significant enriched Gene Ontology terms from the transcriptome, proteome, and metabolome (details in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0126536#pone.0126536.s012" target="_blank">S2 Table</a>).</p><p><sup>x</sup> BEAS-2B up, A549 down</p><p>* BEAS-2B down, A549 up</p><p>Summary of the main HFO- and DF-particle exposure effects.</p
Effects of shipping particles on lung cells.
<p>The net effects from the particles were referenced against the gaseous phase of the emissions. (A) Number of the regulated components in the transcriptome shows more genes regulated by the DF than the HFO particles (in BEAS-2B cells). Similar results were observed for the proteome (B) and metabolome (C) (in A549 cells). (D) Meta-analyses for the transcriptome and proteome using the combined Gene Ontology (GO) term analysis of the 10% most regulated transcripts and proteins. Individual GO terms are listed in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0126536#pone.0126536.s012" target="_blank">S2 Table</a>; the hierarchical pathways are indicated on the right. (E) Gene regulation of Wiki-pathway bioactivation; (F) gene regulation of Wiki-pathway inflammation; g, secreted metabolites; and h, metabolic flux measurements using <sup>13</sup>C-labelled glucose. For all experiments, n = 3.</p
Chemical and physical aerosol characterisation.
<p>(A) The ship diesel engine was operated for 4 h in accordance with the IMO-test cycle. (B) Approximately 28 ng/cm<sup>2</sup> and 56 ng/cm<sup>2</sup> were delivered to the cells from DF and HFO, respectively, with different size distributions. The HFO predominantly contained particles <50 nm, and the DF predominantly contained particles >200 nm, both in mass and number. (C) Number of chemical species in the EA particles. (D) Transmission electron microscope (TEM) images and energy-dispersive X-ray (EDX) spectra of DF-EA and HFO-EA; heavy elements (black speckles, arrow); and contributions of the elements V, P, Fe and Ni in the HFO particles using EDX (* = grid-material). (E) Exemplary EA concentrations (right) and concentration ratios (left) for particulate matter-bound species. For all experiments, n = 3.</p