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  • Avela, Henri F.; Siren, Heli (2020)
    The review concentrates on the properties of analytical and statistical ultrahigh-performance liquid chromatographic (UHPLC) - mass spectrometric (MS) methods suitable for glycero-, glycerophospho- and sphingolipids in lipidomics published between the years 2017 2019. Trends and fluctuations of conventional and nano-UHPLC methods with MS and tandem MS detection were observed in context of analysis conditions and tools used for data-analysis. Whereas general workflow characteristics are agreed upon, more details related to the chromatographic methodology (i.e. stationary and mobile phase conditions) need evidently agreements. Lipid quantitation relies upon isotope-labelled standards in targeted analyses and fully standardless algorithm-based untargeted analyses. Furthermore, a wide spectrum of setups have shown potential for the elucidation of complex and large datasets by minimizing the risks of systematic misinterpretation like false positives. This kind of evaluation was shown to have increased importance and usage for cross-validation and data-analysis. (C) 2020 Elsevier B.V. All rights reserved.
  • Avela, Henri F.; Siren, Heli (2020)
    The present article examines recently published literature on lipids, mainly focusing on research involving glycero-, glycerophospho- and sphingo-lipids. The primary aim is identification of distinct profiles in biologic lipidomic systems by ultra-high-performance liquid chromatography (UHPLC) coupled with mass spectrometry (MS, tandem MS) with multivariate data analysis. This review specifically targets lipid biomarkers and disease pathway mechanisms in humans and artificial targets. Different specimen matrices such as primary blood derivatives (plasma, serum, erythrocytes, and blood platelets), faecal matter, urine, as well as biologic tissues (liver, lung and kidney) are highlighted.
  • Kauppila, T. J.; Flink, A.; Pukkila, J.; Ketola, R. A. (2016)
    RATIONALE: Fast methods that allow the in situ analysis of explosives from a variety of surfaces are needed in crime scene investigations and home-land security. Here, the feasibility of the ambient mass spectrometry technique desorption atmospheric pressure photoionization (DAPPI) in the analysis of the most common nitrogen-based explosives is studied. METHODS: DAPPI and desorption electrospray ionization (DESI) were compared in the direct analysis of trinitrotoluene (TNT), trinitrophenol (picric acid), octogen (HMX), cyclonite (RDX), pentaerythritol tetranitrate (PETN), and nitroglycerin (NG). The effect of different additives in DAPPI dopant and in DESI spray solvent on the ionization efficiency was tested, as well as the suitability of DAPPI to detect explosives from a variety of surfaces. RESULTS: The analytes showed ions only in negative ion mode. With negative DAPPI, TNT and picric acid formed deprotonated molecules with all dopant systems, while RDX, HMX, PETN and NG were ionized by adduct formation. The formation of adducts was enhanced by addition of chloroform, formic acid, acetic acid or nitric acid to the DAPPI dopant. DAPPI was more sensitive than DESI for TNT, while DESI was more sensitive for HMX and picric acid. CONCLUSIONS: DAPPI could become an important method for the direct analysis of nitroaromatics from a variety of surfaces. For compounds that are thermally labile, or that have very low vapor pressure, however, DESI is better suited. Copyright (C) 2016 John Wiley & Sons, Ltd.
  • Pöhö, Paivi; Scholz, Karen; Kärkkäinen, Niina; Haapala, Markus; Räikkönen, Heikki; Kostiainen, Risto; Vaikkinen, Anu (2019)
    A new heated capillary photoionization (CPI) ion source design was developed to photoionize analytes inside a transfer capillary between a gas chromatograph (GC) and a mass spectrometer (MS). The CPI setup included a wide, oval-shaped vacuum-ultraviolet (VUV) transparent magnesium fluoride (MgF2) window to maximize photoionization efficiency and thus sensitivity. The source contained a nitrogen housing around the ionization chamber inlet to avoid undesirable hydrolysis and oxidation reactions with ambient air and to maximize the proportion of formed molecular radical cations of analytes. The feasibility of the ion source was studied by analyzing 18 endogenous steroids in urine as their trimethylsilyl (TMS) derivatives with gas chromatography-tandem mass spectrometry (GC-MS/MS). The method was validated and applied to human urine samples. To our best knowledge, this is the first time that a capillary photoionization ion source has been applied for quantitative analysis of biological samples. The GC-CPI-MS/MS method showed good chromatographic resolution (peak half-widths between 3.1 to 5.3 s), acceptable linearity (coefficient of determination between 0.981 to 0.996), and repeatability (relative standard deviation (RSD%) between 5 to 18%). Limits of detection (LOD) were between 2 to 100 pg mL(-1) and limits of quantitation (LOQ) were between 0.05 to 2 ng mL(-1). In total, 15 steroids were quantified either as a free steroid or glucuronide conjugate from the urine of volunteers. The new CPI source design showed excellent sensitivity for analysis of steroids in complex biological samples. (C) 2019 Elsevier B.V. All rights reserved.
  • Knuuttila, Matias; Hämäläinen, Esa; Poutanen, Matti (2019)
    Recent development of gas chromatography and liquid chromatography-tandem mass spectrometry (GC-MS/MS, LC-MS/MS) has provided novel tools to define sex steroid concentrations. These new methods overcome several of the problems associated with immunoassays for sex steroids. With the novel MS-based applications we are now able to measure small concentrations of the steroid hormones reliably and with high accuracy in both body fluids and tissue homogenates. The sensitivity of the tandem mass spectrometry assays allows us also for the first time to reliably measure picomolar or even femtomolar concentrations of estrogens and androgens. Furthermore, due to a high sensitivity and specificity of MS technology, we are also able to measure low concentrations of steroid hormones of interest in the presence of pharmacological concentration of other steroids and structurally closely related compounds. Both of these features are essential for multiple preclinical models for prostate cancer. The MS assays are also valuable for the simultaneous measurement of multiple steroids and their metabolites in small sample volumes in serum and tissue biopsies of prostate cancer patients before and after drug interventions. As a result, novel information about steroid hormone synthesis and metabolic pathways in prostate cancer has been obtained. In our recent studies, we have extensively applied a GC-MS/MS method to study androgen biosynthesis and metabolism in VCaP prostate cancer xenografts in mice. In the present review, we shortly summarize some of the benefits of the GC-MS/MS and novel LC-MS/MS assays, and provide examples of their use in defining novel mechanisms of androgen action in prostate cancer.
  • Kauhanen, Dimple; Sysi-Aho, Marko; Koistinen, Kaisa M.; Laaksonen, Reijo; Sinisalo, Juha; Ekroos, Kim (2016)
    Monitoring the levels of the ceramides (Cer) d18:1/16:0, Cer d18:1/18:0, Cer d18:1/24:0, and Cer d18:1/24:1 and ratios thereof in human plasma empowers the prediction of fatal outcome of coronary artery disease (CAD). We describe a validated liquid chromatography-tandem mass spectrometry (LC-MS/MS) methodology for clinical-scaled measurement of the four distinct ceramides. Rapid plasma precipitation was accomplished in 96-well format. Excellent extraction recoveries in the range of 98-109 % were achieved for each ceramide. Addition of corresponding D-7-labeled ceramide standards facilitated precise quantification of each plasma ceramide species utilizing a novel short 5-min LC-MS/MS method. Neither matrix interference nor carryover was observed. Robust intra- and inter-assay accuracy and precision <15 % at five different concentrations were obtained. Linear calibration lines with regressions, R (2) > 0.99, were achieved for all analytes. Short-term bench top, long-term plasma, and extract stability demonstrated that the distinct ceramides were stable in the conditions evaluated. The validity of the methodology was demonstrated by determining the precise ceramide concentrations in a small CAD case-control study. Thus, our LC-MS/MS methodology features simple sample preparation and short analysis time for accurate quantification of Cer d18:1/16:0, Cer d18:1/18:0, Cer d18:1/24:0, and Cer d18:1/24:1, designed for routine analysis.
  • Yrjönen, Teijo; Vuorela, Heikki; Kauppila, Tiina J. (2017)
    Desorption atmospheric pressure photoionization (DAPPI) is an ambient mass spectrometry (MS) technique that can be used for the analysis of polar and nonpolar compounds directly from surfaces. Here, the feasibility of DAPPI-MS in the screening of plant metabolites from dried Peucedanum palustre leaves and umbels was studied. DAPPI-MS requires no prior sample preparation or chromatographic separation, and the analysis can therefore be performed directly from the untreated plant material. P. palustre contains several linear and angular furanocoumarins, some of which are specific for the species. The DAPPI mass spectra of both leaf and umbel samples showed distinct ions at m/z 445 and 443 in positive and negative ion modes, respectively. MS2 analyses of these ions confirmed that the ions were the protonated and deprotonated molecules, respectively, of peulustrin and its isomers, which have only been identified from P. palustre. The direct analysis of dried plant material by DAPPI-MS was shown to provide a fast and reliable means to confirm the identity of plant materials, to study the metabolite profiles of plants, and to screen biologically relevant compounds from plant surfaces.
  • Zhang, Lu; Diaz-Diaz, Norberto; Zarringhalam, Kourosh; Hermansson, Martin; Somerharju, Pentti; Chuang, Jeffrey (2012)
  • Dällenbach, Kaspar; Kourtchev, Ivan; Vogel, Alexander L.; Bruns, Emily A.; Jiang, Jianhui; Petäjä, Tuukka; Jaffrezo, Jean-Luc; Aksoyoglu, Sebnem; Kalberer, Markus; Baltensperger, Urs; El Haddad, Imad; Prevot, Andre S. H. (2019)
    This study presents the molecular composition of organic aerosol (OA) using ultra-high-resolution mass spectrometry (Orbitrap) at an urban site in Central Europe (Zurich, Switzerland). Specific source spectra were also analysed, including samples representative of woodburning emissions from Alpine valleys during wood-burning pollution episodes and smog chamber investigations of woodsmoke, as well as samples from Hyytiala, which were strongly influenced by biogenic secondary organic aerosol. While samples collected during winter in Alpine valleys have a molecular composition remarkably similar to fresh laboratory wood-burning emissions, winter samples from Zurich are influenced by more aged wood-burning emissions. In addition, other organic aerosol emissions or formation pathways seem to be important at the latter location in winter. Samples from Zurich during summer are similar to those collected in Hyytiala and are predominantly impacted by oxygenated compounds with an H/C ratio of 1.5, indicating the importance of biogenic precursors for secondary organic aerosol (SOA) formation at this location (summertime Zurich - carbon number 7.6, O : C 0.7; Hyytiala - carbon number 10.5, O : C 0.57). We could explain the strong seasonality of the molecular composition at a typical European site by primary and aged wood-burning emissions and biogenic secondary organic aerosol formation during winter and summer, respectively. Results presented here likely explain the rather constant seasonal predominance of non-fossil organic carbon at European locations.
  • Dickinson, Amy; Saraswat, Mayank; Joenväärä, Sakari; Agarwal, Rahul; Jyllikoski, Daniel; Wilkman, Tommy; Mäkitie, Antti; Silen, Suvi (2020)
    Lipid metabolic reprogramming is one hallmark of cancer. Lipid metabolism is regulated by numerous enzymes, many of which are targeted by several drugs on the market. We aimed to characterize the lipid alterations in oral squamous cell carcinoma (OSCC) as a basis for understanding its lipid metabolism, thus identifying potential therapeutic targets. We compared lipid species, classes, and glycerophospholipid (GPL) fatty acid species between paired tumor tissue and healthy oral tongue mucosa samples from 10 OSCC patients using a QExactive mass spectrometer. After filtering the 1370 lipid species identified, we analyzed 349 species: 71 were significantly increased in OSCC. The GPL metabolism pathway was most represented by the lipids differing in OSCC (P = .005). Cholesterol and the GPLs phosphatidylcholines, phosphatidylethanolamines, and phosphatidylinositols were most significantly increased in OSCC tissue (FC 1.8, 2.0, 2.1, and 2.3 and, P = .003, P = .005, P = .002, P = .007). In conclusion, we have demonstrated a shift in the lipid metabolism in these OSCC samples by characterizing the detailed landscape. Predominantly, cholesterol and GPL metabolism were altered, suggesting that interactions with sterol regulatory binding proteins may be involved. The FA composition changes of the GPLs suggest increased de novo lipogenesis.
  • Tigistu-Sahle, Feven; Lampinen, Milla; Kilpinen, Lotta; Holopainen, Minna; Lehenkari, Petri; Laitinen, Saara; Käkelä, Reijo (2017)
    High arachidonic acid (20:4n-6) and low n-3 PUFA levels impair the capacity of cultured human bone marrow mesenchymal stromal cells (hBMSCs) to modulate immune functions. The capacity of the hBMSCs to modify PUFA structures was found to be limited. Therefore, different PUFA supplements given to the cells resulted in very different glycerophospholipid (GPL) species profiles and substrate availability for phospholipases, which have preferences for polar head group and acyl chains when liberating PUFA precursors for production of lipid mediators. When supplemented with 20:4n-6, the cells increased prostaglandin E2 secretion. However, they elongated 20:4n-6 to the less active precursor, 22:4n-6, and also incorporated it into triacylglycerols, which may have limited the proinflammatory signaling. The n-3 PUFA precursor, 18:3n-3, had little potency to reduce the GPL 20:4n-6 content, while the eicosapentaenoic (20:5n-3) and docosahexaenoic (22:6n-3) acid supplements efficiently displaced the 20:4n-6 acyls, and created diverse GPL species substrate pools allowing attenuation of inflammatory signaling.(Jlr) The results emphasize the importance of choosing appropriate PUFA supplements for in vitro hBMSC expansion and suggests that for optimal function they require an exogenous fatty acid source providing 20:5n-3 and 22:6n-3 sufficiently, but 20:4n-6 moderately, which calls for specifically designed optimal PUFA supplements for the cultures.
  • Ryding, Mauritz J.; Giuliani, Alexandre; Patanen, Minna; Niskanen, Johannes; Simoes, Grazieli; Miller, Glenn B. S.; Antonsson, Egill; Jokinen, Tuija; Miron, Catalin; Björneholm, Olle; Hansen, Klavs; Borve, Knut J.; Uggerud, Einar (2014)