Petroleomic Analysis of Bio-oils from the Fast Pyrolysis of Biomass: Laser Desorption Ionization−Linear Ion Trap−Orbitrap Mass Spectrometry Approach

Fast pyrolysis of biomass produces bio-oils that can be upgraded into biofuels. Despite similar physical properties to petroleum, the chemical properties of bio-oils are quite different and their chemical compositions, particularly those of non-volatile compounds, are not well-known. Here, we report the first time attempt at analyzing bio-oils using high-resolution mass spectrometry (MS), which employed laser desorption ionization−linear ion trap−Orbitrap MS. Besides a few limitations, we could determine chemical compositions for over 100 molecular compounds in a bio-oil sample produced from the pyrolysis of a loblolly pine tree. These compounds consist of 3−6 oxygens and 9−17 double-bond equivalents (DBEs). Among those, O4 compounds with a DBE of 9−13 were most abundant. Unlike petroleum oils, the lack of nearby molecules within a ±2 Da mass window for major components enabled clear isolation of precursor ions for subsequent MS/MS structural investigations. Petroleomic analysis and a comparison to low-mass components in hydrolytic lignin suggest that they are dimers and trimers of depolymerized lignin

High-Resolution Mass Spectrometric Characterization of Molecules on Biochar from Pyrolysis and Gasification of Switchgrass

Organic molecules entrapped in biochar during pyrolysis and gasification of switchgrass have been studied using high-resolution mass spectrometry. Two solvent systems, toluene and a mixture of water/methanol, were used to extract hydrophobic aromatic compounds and hydrophilic polar compounds, respectively. Laser desorption ionization and atmospheric pressure photoionization were used for toluene extracts, while electrospray ionization was used for water/methanol extracts, followed by orbitrap mass spectrometric data acquisition. Molecular compounds previously known in bio-oils were observed for fast pyrolysis biochar, with phenolic and carbohydrate-derived compounds originating from the pyrolysis of lignin and holocellulose, respectively. In contrast, polycyclic aromatic hydrocarbons (PAHs) with various ring sizes were observed for gasification biochar and also for slow pyrolysis biochar in low abundance

3D MALDI Mass Spectrometry Imaging of a Single Cell: Spatial Mapping of Lipids in the Embryonic Development of Zebrafish

The zebrafish (Danio rerio) has been widely used as a model vertebrate system to study lipid metabolism, the roles of lipids in diseases, and lipid dynamics in embryonic development. Here, we applied high-spatial resolution matrix-assisted laser desorption/ionization (MALDI)-mass spectrometry imaging (MSI) to map and visualize the three-dimensional spatial distribution of phospholipid classes, phosphatidylcholine (PC), phosphatidylethanolamines (PE), and phosphatidylinositol (PI), in newly fertilized individual zebrafish embryos. This is the first time MALDI-MSI has been applied for three dimensional chemical imaging of a single cell. PC molecular species are present inside the yolk in addition to the blastodisc, while PE and PI species are mostly absent in the yolk. Two-dimensional MSI was also studied for embryos at different cell stages (1-, 2-, 4-, 8-, and 16-cell stage) to investigate the localization changes of some lipids at various cell developmental stages. Four different normalization approaches were compared to find reliable relative quantification in 2D- and 3D- MALDI MSI data sets

Three-Dimensional Profiling of OLED by Laser Desorption Ionization-Mass Spectrometry Imaging

Organic light emitting devices (OLEDs), especially in a screen display format, present unique and interesting substrates for Laser Desorption/Ionization - Mass Spectrometry Imaging (LDI-MSI) analysis. These devices contain many compounds that inherently absorb light energy and do not require an additional matrix to induce desorption and ionization. OLED screens have lateral features with dimensions that are tens of microns in magnitude and depth features that are tens to hundreds of nanometers thick. Monitoring the chemical composition of these features is essential, as contamination and degradation can impact device lifetime. This work demonstrates the capability of LDI-MSI to obtain lateral and partial depth resolved information of multicolored OLED displays and suggests the application to other mixed organic electronics with minimal sample preparation. This was realized when analyzing two different manufactured OLEDs, in an active-matrix display format, with-out the need to remove the cathode. By utilizing low laser energy and high lateral spatial resolution imaging (10 µm), depth profiling can be observed while maintaining laterally resolved information resulting in a three-dimensional MSI approach that would complement existing OLED characterization methods

Increased Risk of Ischemic Stroke during Sleep in Apneic Patients.

BACKGROUND AND PURPOSE:The literature indicates that obstructive sleep apnea (OSA) increases the risk of ischemic stroke. However, the causal relationship between OSA and ischemic stroke is not well established. This study examined whether preexisting OSA symptoms affect the onset of acute ischemic stroke. METHODS:We investigated consecutive patients who were admitted with acute ischemic stroke, using a standardized protocol including the Berlin Questionnaire on symptoms of OSA prior to stroke. The collected stroke data included the time of the stroke onset, risk factors, and etiologic subtypes. The association between preceding OSA symptoms and wake-up stroke (WUS) was assessed using multivariate logistic regression analysis. RESULTS:We identified 260 subjects with acute ischemic strokes with a definite onset time, of which 25.8% were WUS. The presence of preexisting witnessed or self-recognized sleep apnea was the only risk factor for WUS (adjusted odds ratio=2.055, 95% confidence interval=1.035-4.083, p=0.040). CONCLUSIONS:Preexisting symptoms suggestive of OSA were associated with the occurrence of WUS. This suggests that OSA contributes to ischemic stroke not only as a predisposing risk factor but also as a triggering factor. Treating OSA might therefore be beneficial in preventing stroke, particularly that occurring during sleep

Toward Mass Spectrometry Imaging in the Metabolomics Scale: Increasing Metabolic Coverage Through Multiple On-Tissue Chemical Modifications

Exploring the metabolic differences directly on tissues is essential for the comprehensive understanding of how multicellular organisms function. Mass spectrometry imaging (MSI) is an attractive technique toward this goal; however, MSI in metabolomics scale has been hindered by multiple limitations. This is most notable for single cell level high-spatial resolution imaging because of the limited number of molecules in small sampling size and the low ionization yields of many metabolites. Several on-tissue chemical derivatization approaches have been reported to increase MSI signals of targeted compounds, especially in matrix-assisted laser desorption/ionization (MALDI)- MSI. Herein, we adopt a combination of chemical derivatization reactions, to selectively enhance metabolite signals of a specific functional group for each consecutive tissue section. Three well-known on-tissue derivatization methods were used as a proof of concept experiment: coniferyl aldehyde for primary amines, Girard’s reagent T for carbonyl groups, and 2-picolylamine for carboxylic acids. This strategy was applied to the cross-sections of leaves and roots from two different maize genotypes (B73 and Mo17), and enabled the detection of over six hundred new unique metabolite features compared to without modification. Statistical analysis indicated quantitative variation between metabolites in the tissue sections, while MS images revealed differences in localization of these metabolites. Combined, this untargeted approach facilitated the visualization of various classes of compounds, demonstrating the potential for untargeted MSI in the metabolomics scale