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  1. Article: Strukturbezogene religionspsychologische Diagnostik

    Trettin, Alexander

    Trauma & Gewalt

    2022  Volume 16, Issue 3, Page(s) 218–230

    Abstract: Auf der Basis des Formates der strukturbezogenen Religionspsychologie wurde das Verfahren der strukturbezogenen religionspsychologischen Diagnostik entwickelt, bei dem verschiedene Erhebungs- und Analysemethoden im Sinne des Methodenpluralismus (Mixed ... ...

    Title translation Structurally related religion-psychological diagnostics
    Abstract Auf der Basis des Formates der strukturbezogenen Religionspsychologie wurde das Verfahren der strukturbezogenen religionspsychologischen Diagnostik entwickelt, bei dem verschiedene Erhebungs- und Analysemethoden im Sinne des Methodenpluralismus (Mixed Methods) je nach Bedarf miteinander kombiniert werden können. In diesem Artikel soll dieses Verfahren vorgestellt und durch einzelne Fallbeispiele aus der therapeutischen Arbeit mit traumatisierten Geflüchteten kontrastiert werden. Für die vorliegende Studie, bei der vier männliche Probanden befragt wurden, kamen folgende Methoden zum Einsatz: zur Erfassung der Religiosität bzw. der Spiritualität die Zentralitätsskala, zur Anamnese und Exploration das narrativ-diagnostische Interview, für die Auswertung die Narrationsanalyse sowie die diagnostische Bilanz (OPD-2) und zur Erfassung von Traumasymptomen die Impact of Event Scale (IES-R)
    Keywords Diagnosis ; Diagnostik ; Erzählungen ; Flüchtlinge ; Interviews ; Narratives ; Refugees ; Religion ; Religiosity ; Religiosität ; Spirituality ; Spiritualität ; Trauma
    Language German
    Document type Article
    ISSN 1863-7167
    ISSN 1863-7167
    DOI 10.21706/tg-16-3-218
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  2. Article: Psychodrama als Verfahren innerhalb der religionspsychologischen Praxis. Exemplifiziert an der psychodramatischen Lesung des 'Zauberbergs'

    Trettin, Alexander

    cultura & psyché

    2021  Volume 2, Issue 2, Page(s) 197–211

    Abstract: Der Beitrag beschreibt, wie Psychodrama als Verfahren innerhalb der religionspsychologischen Praxis empirisch eingesetzt werden kann, um religiöse/spirituelle Strukturen sichtbar bzw. religiöse/spirituelle Phänomene begreifbar zu machen. Hierbei gilt es, ...

    Title translation Psychodrama as a process within the practice of the psychology of religion. Exemplified by the psychodramatic reading of the 'Magic Mountain'
    Abstract Der Beitrag beschreibt, wie Psychodrama als Verfahren innerhalb der religionspsychologischen Praxis empirisch eingesetzt werden kann, um religiöse/spirituelle Strukturen sichtbar bzw. religiöse/spirituelle Phänomene begreifbar zu machen. Hierbei gilt es, Religiosität bzw. Spiritualität als therapeutische Ressource herauszuarbeiten. Im Artikel werden zudem die religionspsychologischen Anteile des Psychodramas skizziert, die schließlich in Überlegungen zum Ritual und zur Katharsis münden. Die psychodramatische Lesung des 'Zauberbergs' von vier Freimaurern dient hierbei als Fallbeispiel für die praktische Anwendung.
    Keywords Literatur ; Literature ; Psychodrama ; Psychotherapeutic Processes ; Psychotherapeutic Techniques ; Psychotherapeutische Prozesse ; Psychotherapeutische Techniken ; Role Playing ; Rollenspiel ; Spirituality ; Spiritualität
    Language German
    Document type Article
    DOI 10.1007/s43638-022-00037-z
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  3. Article ; Online: Synthetic dyes: A mass spectrometry approach and applications.

    Millbern, Zoe / Trettin, Alison / Wu, Rachel / Demmler, Morgan / Vinueza, Nelson R

    Mass spectrometry reviews

    2022  Volume 43, Issue 2, Page(s) 327–344

    Abstract: Synthetic dyes are found in a wide variety of applications today, including but not limited to textiles, foods, and medicine. The analysis of these molecules is pertinent to several fields such as forensics, environmental monitoring, and quality control, ...

    Abstract Synthetic dyes are found in a wide variety of applications today, including but not limited to textiles, foods, and medicine. The analysis of these molecules is pertinent to several fields such as forensics, environmental monitoring, and quality control, all of which require the sensitivity and selectivity of analysis provided by mass spectrometry (MS). Recently, there has been an increase in the implementation of MS evaluation of synthetic dyes by various methods, with the majority of research thus far falling under electrospray ionization and moving toward direct ionization methods. This review covers an overview of the chemistry of synthetic dyes needed for the understanding of MS sample preparation and spectral results, current fields of application, ionization methods, and fragmentation trends and works that have been reported in recent years.
    Language English
    Publishing date 2022-11-10
    Publishing country United States
    Document type Journal Article ; Review
    ZDB-ID 1491946-1
    ISSN 1098-2787 ; 0277-7037
    ISSN (online) 1098-2787
    ISSN 0277-7037
    DOI 10.1002/mas.21818
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  4. Article ; Online: LC-MS/MS analysis of uncommon paracetamol metabolites derived through in vitro polymerization and nitration reactions in liquid nitrogen.

    Trettin, Arne / Jordan, Jens / Tsikas, Dimitrios

    Journal of chromatography. B, Analytical technologies in the biomedical and life sciences

    2014  Volume 966, Page(s) 171–178

    Abstract: Paracetamol (acetaminophen, APAP) is a commonly used analgesic drug. Known paracetamol metabolites include the glucuronide, sulfate and mercapturate. N-Acetyl-benzoquinonimine (NAPQI) is considered the toxic intermediate metabolite of paracetamol. In ... ...

    Abstract Paracetamol (acetaminophen, APAP) is a commonly used analgesic drug. Known paracetamol metabolites include the glucuronide, sulfate and mercapturate. N-Acetyl-benzoquinonimine (NAPQI) is considered the toxic intermediate metabolite of paracetamol. In vitro and in vivo studies indicate that paracetamol is also metabolized to additional poorly characterized metabolites. For example, metabolomic studies in urine samples of APAP-treated mice revealed metabolites such as APAP-sulfate-APAP and APAP-S-S-APAP in addition to the classical phase II metabolites. Here, we report on the development and application of LC-MS and LC-MS/MS approaches to study reactions of unlabelled and (2)H-labelled APAP with unlabelled and (15)N-labelled nitrite in aqueous phosphate buffers (pH 7.4) upon their immersion into liquid nitrogen (-196°C). In mechanistic studies, these reactions were also studied in aqueous buffer prepared in (18)O-labelled water. LC-MS and LC-MS/MS analyses were performed on a reverse-phase material (C18) using gradient elution (2mM ammonium acetate/acetonitrile), in positive and negative electrospray mode. We identified a series of APAP metabolites including di-, tri- and tetra-APAP, mono- and di-nitro-APAP and nitric ester of di-APAP. Our study indicates that nitrite induces oxidation, i.e., polymerization and nitration of APAP, when buffered APAP/nitrite solutions are immersed into liquid nitrogen. These reactions are specific for nitrite with respect to nitrate and do not proceed via intermediate formation of NAPQI. Potassium ions and physiological saline but not thiols inhibit nitrite- and shock-freeze-induced reactions of paracetamol. The underlying mechanism likely involves in situ formation of NO2 radicals from nitrite secondary to profound pH reduction (down to pH 1) and disproportionation. Polymeric paracetamol species can be analyzed as pentafluorobenzyl derivatives by LC-MS but not by GC-MS.
    MeSH term(s) Acetaminophen/analogs & derivatives ; Acetaminophen/chemistry ; Animals ; Chromatography, Liquid/methods ; Humans ; Mice ; Nitric Oxide/chemistry ; Nitrogen/chemistry ; Polymerization ; Tandem Mass Spectrometry/methods
    Chemical Substances Nitric Oxide (31C4KY9ESH) ; Acetaminophen (362O9ITL9D) ; Nitrogen (N762921K75)
    Language English
    Publishing date 2014-09-01
    Publishing country Netherlands
    Document type Journal Article
    ZDB-ID 1180823-8
    ISSN 1873-376X ; 0378-4347 ; 1570-0232 ; 1387-2273
    ISSN (online) 1873-376X
    ISSN 0378-4347 ; 1570-0232 ; 1387-2273
    DOI 10.1016/j.jchromb.2013.11.055
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  5. Article: LC–MS/MS analysis of uncommon paracetamol metabolites derived through in vitro polymerization and nitration reactions in liquid nitrogen

    Trettin, Arne / Dimitrios Tsikas / Jens Jordan

    Journal of Chromatography B. 2014 Sept. 01, v. 966

    2014  

    Abstract: Paracetamol (acetaminophen, APAP) is a commonly used analgesic drug. Known paracetamol metabolites include the glucuronide, sulfate and mercapturate. N-Acetyl-benzoquinonimine (NAPQI) is considered the toxic intermediate metabolite of paracetamol. In ... ...

    Abstract Paracetamol (acetaminophen, APAP) is a commonly used analgesic drug. Known paracetamol metabolites include the glucuronide, sulfate and mercapturate. N-Acetyl-benzoquinonimine (NAPQI) is considered the toxic intermediate metabolite of paracetamol. In vitro and in vivo studies indicate that paracetamol is also metabolized to additional poorly characterized metabolites. For example, metabolomic studies in urine samples of APAP-treated mice revealed metabolites such as APAP-sulfate-APAP and APAP-S-S-APAP in addition to the classical phase II metabolites. Here, we report on the development and application of LC–MS and LC–MS/MS approaches to study reactions of unlabelled and 2H-labelled APAP with unlabelled and 15N-labelled nitrite in aqueous phosphate buffers (pH 7.4) upon their immersion into liquid nitrogen (−196°C). In mechanistic studies, these reactions were also studied in aqueous buffer prepared in 18O-labelled water. LC–MS and LC–MS/MS analyses were performed on a reverse-phase material (C18) using gradient elution (2mM ammonium acetate/acetonitrile), in positive and negative electrospray mode. We identified a series of APAP metabolites including di-, tri- and tetra-APAP, mono- and di-nitro-APAP and nitric ester of di-APAP. Our study indicates that nitrite induces oxidation, i.e., polymerization and nitration of APAP, when buffered APAP/nitrite solutions are immersed into liquid nitrogen. These reactions are specific for nitrite with respect to nitrate and do not proceed via intermediate formation of NAPQI. Potassium ions and physiological saline but not thiols inhibit nitrite- and shock-freeze-induced reactions of paracetamol. The underlying mechanism likely involves in situ formation of NO2 radicals from nitrite secondary to profound pH reduction (down to pH 1) and disproportionation. Polymeric paracetamol species can be analyzed as pentafluorobenzyl derivatives by LC–MS but not by GC–MS.
    Keywords acetaminophen ; acetonitrile ; ammonium acetate ; buffers ; cations ; free radicals ; gas chromatography-mass spectrometry ; in vivo studies ; liquid chromatography ; metabolites ; metabolomics ; mice ; nitrites ; nitrogen ; nitrogen dioxide ; oxidation ; pH ; phosphates ; polymerization ; potassium ; sulfates ; thiols ; toxicity ; urine
    Language English
    Dates of publication 2014-0901
    Size p. 171-178.
    Publishing place Elsevier B.V.
    Document type Article
    ISSN 1570-0232
    DOI 10.1016/j.jchromb.2013.11.055
    Database NAL-Catalogue (AGRICOLA)

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  6. Article ; Online: Trapping of NAPQI, the intermediate toxic paracetamol metabolite, by aqueous sulfide (S²⁻) and analysis by GC-MS/MS.

    Trettin, Arne / Batkai, Sandor / Thum, Thomas / Jordan, Jens / Tsikas, Dimitrios

    Journal of chromatography. B, Analytical technologies in the biomedical and life sciences

    2014  Volume 963, Page(s) 99–105

    Abstract: NAPQI, i.e., N-acetyl-p-benzoquinone imine, is considered the toxic metabolite of the widely used analgesic drug paracetamol (acetaminophen, APAP). Due to its high reactivity towards nucleophiles both in low- and high-molecular-mass biomolecules, NAPQI ... ...

    Abstract NAPQI, i.e., N-acetyl-p-benzoquinone imine, is considered the toxic metabolite of the widely used analgesic drug paracetamol (acetaminophen, APAP). Due to its high reactivity towards nucleophiles both in low- and high-molecular-mass biomolecules, NAPQI is hardly detectable in its native form. Upon conjugation with glutathione, NAPQI is finally excreted in the urine as the paracetamol mercapturic acid. Thus, determination of paracetamol mercapturate may provide a measure of in vivo NAPQI formation. In this work, we propose the use of Na2S in aqueous solution to trap NAPQI and to analyze the reaction product, i.e., 3-thio-paracetamol, together with paracetamol by GC-MS/MS in the electron-capture negative-ion chemical ionization mode after solvent extraction with ethyl acetate and derivatization with pentafluorobenzyl bromide. In mechanistic studies, we used newly synthesized N-acetyl-p-[2,3,5,6-(2)H4]benzoquinone imine (d4-NAPQI). In quantitative analyses, N-(4-hydroxyphenyl)-[2,3,5,6-(2)H4]acetamide (d4-APAP) was used as the internal standard both for NAPQI and APAP. 3-Thio-d3-paracetamol, prepared from d4-NAPQI and Na2S, may also be useful as an internal standard. We showed NAPQI in vitro formation from APAP by recombinant cyclooxygenase-1 as well as by dog liver homogenate. In vivo formation of NAPQI was demonstrated in mice given paracetamol intraperitoneally (about 150 mg/kg).
    MeSH term(s) Acetaminophen/analogs & derivatives ; Acetaminophen/metabolism ; Analgesics, Non-Narcotic/chemistry ; Analgesics, Non-Narcotic/metabolism ; Animals ; Benzoquinones/analysis ; Benzoquinones/metabolism ; Cyclooxygenase 1/metabolism ; Dogs ; Gas Chromatography-Mass Spectrometry ; Imines/analysis ; Imines/metabolism ; Liver/metabolism ; Male ; Mice ; Mice, Inbred C57BL ; Recombinant Proteins/metabolism ; Sulfides/chemistry ; Tandem Mass Spectrometry ; Water/chemistry
    Chemical Substances Analgesics, Non-Narcotic ; Benzoquinones ; Imines ; Recombinant Proteins ; Sulfides ; Water (059QF0KO0R) ; Acetaminophen (362O9ITL9D) ; Cyclooxygenase 1 (EC 1.14.99.1) ; N-acetyl-4-benzoquinoneimine (G6S9BN13TI) ; sodium sulfide (YGR27ZW0Y7)
    Language English
    Publishing date 2014-07-15
    Publishing country Netherlands
    Document type Journal Article
    ZDB-ID 1180823-8
    ISSN 1873-376X ; 0378-4347 ; 1570-0232 ; 1387-2273
    ISSN (online) 1873-376X
    ISSN 0378-4347 ; 1570-0232 ; 1387-2273
    DOI 10.1016/j.jchromb.2014.05.050
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  7. Article: Trapping of NAPQI, the intermediate toxic paracetamol metabolite, by aqueous sulfide (S2−) and analysis by GC–MS/MS

    Trettin, Arne / Dimitrios Tsikas / Jens Jordan / Sandor Batkai / Thomas Thum

    Journal of Chromatography B. 2014 July 15, v. 963

    2014  

    Abstract: NAPQI, i.e., N-acetyl-p-benzoquinone imine, is considered the toxic metabolite of the widely used analgesic drug paracetamol (acetaminophen, APAP). Due to its high reactivity towards nucleophiles both in low- and high-molecular-mass biomolecules, NAPQI ... ...

    Abstract NAPQI, i.e., N-acetyl-p-benzoquinone imine, is considered the toxic metabolite of the widely used analgesic drug paracetamol (acetaminophen, APAP). Due to its high reactivity towards nucleophiles both in low- and high-molecular-mass biomolecules, NAPQI is hardly detectable in its native form. Upon conjugation with glutathione, NAPQI is finally excreted in the urine as the paracetamol mercapturic acid. Thus, determination of paracetamol mercapturate may provide a measure of in vivo NAPQI formation. In this work, we propose the use of Na2S in aqueous solution to trap NAPQI and to analyze the reaction product, i.e., 3-thio-paracetamol, together with paracetamol by GC–MS/MS in the electron-capture negative-ion chemical ionization mode after solvent extraction with ethyl acetate and derivatization with pentafluorobenzyl bromide. In mechanistic studies, we used newly synthesized N-acetyl-p-[2,3,5,6-2H4]benzoquinone imine (d4-NAPQI). In quantitative analyses, N-(4-hydroxyphenyl)-[2,3,5,6-2H4]acetamide (d4-APAP) was used as the internal standard both for NAPQI and APAP. 3-Thio-d3-paracetamol, prepared from d4-NAPQI and Na2S, may also be useful as an internal standard. We showed NAPQI in vitro formation from APAP by recombinant cyclooxygenase-1 as well as by dog liver homogenate. In vivo formation of NAPQI was demonstrated in mice given paracetamol intraperitoneally (about 150mg/kg).
    Keywords acetaminophen ; aqueous solutions ; benzoquinones ; chromatography ; derivatization ; dogs ; ethyl acetate ; glutathione ; ionization ; liver ; metabolites ; mice ; prostaglandin synthase ; quantitative analysis ; solvents ; sulfides ; toxicity ; urine
    Language English
    Dates of publication 2014-0715
    Size p. 99-105.
    Publishing place Elsevier B.V.
    Document type Article
    ISSN 1570-0232
    DOI 10.1016/j.jchromb.2014.05.050
    Database NAL-Catalogue (AGRICOLA)

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  8. Article ; Online: GC-MS/MS and LC-MS/MS studies on unlabelled and deuterium-labelled oleic acid (C18:1) reactions with peroxynitrite (O=N-O-O⁻) in buffer and hemolysate support the pM/nM-range of nitro-oleic acids in human plasma.

    Trettin, Arne / Böhmer, Anke / Zoerner, Alexander A / Gutzki, Frank-Mathias / Jordan, Jens / Tsikas, Dimitrios

    Journal of chromatography. B, Analytical technologies in the biomedical and life sciences

    2014  Volume 964, Page(s) 172–179

    Abstract: Oleic acid (cis-9,10-octadecenoic acid) is the most abundant monounsaturated fatty acid in human blood. Peroxynitrite (ONOO(-)) is a short-lived species formed from the reaction of nitric oxide (NO) and superoxide (O2(-)). Peroxynitrite is a potent ... ...

    Abstract Oleic acid (cis-9,10-octadecenoic acid) is the most abundant monounsaturated fatty acid in human blood. Peroxynitrite (ONOO(-)) is a short-lived species formed from the reaction of nitric oxide (NO) and superoxide (O2(-)). Peroxynitrite is a potent oxidizing and moderate nitrating agent. We investigated reactions of unlabelled and deuterium labelled oleic acid in phosphate buffered saline (PBS) and lysed human erythrocytes with commercially available sodium peroxynitrite (Na(+)ONOO(-)). Non-derivatized reaction products were analyzed by spectrophotometry, HPLC with UV absorbance detection, and LC-MS/MS electrospray ionization in the negative-ion mode. Reaction products were also analyzed by GC-MS/MS in the electron capture negative-ion chemical ionization mode after derivatization first with pentafluorobenzyl (PFB) bromide and then with N,O-bis(trimethylsilyl)trifluoroacetamide. Identified oleic acid reaction products in PBS and hemolysate include cis-9,10-epoxystearic acid and trans-9,10-epoxystearic acid (about 0.1% with respect to oleic acid), threo- and erythro-9,10-dihydroxy-stearic acids. Vinyl nitro-oleic acids, 9-nitro-oleic acid (9-NO2OA) and 10-nitro-oleic acid (10-NO2OA), or other nitro-oleic acids were not found to be formed from the reaction of oleic acid with peroxynitrite in PBS or hemolysate. Our in vitro study suggests that peroxynitrite oxidizes but does not nitrate oleic acid in biological samples. Unlike thiols and tyrosine, oleic acid is not susceptible to peroxynitrite. GC-MS/MS analysis of PFB esters is by far more efficient than LC-MS/MS analysis of non-derivatized oleic acid and its derivates. Our in vitro results support our previous in vivo findings that nitro-oleic acid plasma concentrations of healthy and diseased subjects are in the pM/nM-range.
    MeSH term(s) Buffers ; Chromatography, High Pressure Liquid ; Deuterium/chemistry ; Erythrocytes/chemistry ; Gas Chromatography-Mass Spectrometry ; Hemolysis ; Humans ; Hydroxylation ; Nitro Compounds/blood ; Nitro Compounds/chemistry ; Oleic Acid/blood ; Oleic Acid/chemistry ; Oxidation-Reduction ; Peroxynitrous Acid/chemistry ; Tandem Mass Spectrometry
    Chemical Substances Buffers ; Nitro Compounds ; Peroxynitrous Acid (14691-52-2) ; Oleic Acid (2UMI9U37CP) ; Deuterium (AR09D82C7G)
    Language English
    Publishing date 2014-08-01
    Publishing country Netherlands
    Document type Journal Article ; Research Support, Non-U.S. Gov't
    ZDB-ID 1180823-8
    ISSN 1873-376X ; 0378-4347 ; 1570-0232 ; 1387-2273
    ISSN (online) 1873-376X
    ISSN 0378-4347 ; 1570-0232 ; 1387-2273
    DOI 10.1016/j.jchromb.2014.01.016
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  9. Article ; Online: In-source formation of N-acetyl-p-benzoquinone imine (NAPQI), the putatively toxic acetaminophen (paracetamol) metabolite, after derivatization with pentafluorobenzyl bromide and GC-ECNICI-MS analysis.

    Tsikas, Dimitrios / Trettin, Arne / Zörner, Alexander A / Gutzki, Frank-Mathias

    Journal of chromatography. B, Analytical technologies in the biomedical and life sciences

    2011  Volume 879, Issue 17-18, Page(s) 1476–1484

    Abstract: Pentafluorobenzyl (PFB) bromide (PFB-Br) is a versatile derivatization reagent for numerous classes of compounds. Under electron-capture negative-ion chemical ionization (ECNICI) conditions PFB derivatives of acidic compounds readily and abundantly ... ...

    Abstract Pentafluorobenzyl (PFB) bromide (PFB-Br) is a versatile derivatization reagent for numerous classes of compounds. Under electron-capture negative-ion chemical ionization (ECNICI) conditions PFB derivatives of acidic compounds readily and abundantly ionize to produce intense anions due to [M-PFB](-). In the present article we investigated the PFB-Br derivatization of unlabelled acetaminophen (N-acetyl-p-aminophenol, NAPAP-d(0); paracetamol; MW 151) and tetradeuterated acetaminophen (NAPAP-d(4); MW 155) in anhydrous acetonitrile and their GC-ECNICI-MS behavior using methane as the buffer gas. In addition to the expected anions [M-PFB](-) at m/z 150 from NAPAP-d(0) and m/z 154 from NAPAP-d(4), we observed highly reproducibly almost equally intense anions at m/z 149 and m/z 153, respectively. Selected ion monitoring of these ions is suitable for specific and sensitive quantification of acetaminophen in human plasma and urine. Detailed investigations suggest in-source formation of N-acetyl-p-benzoquinone imine (NAPQI; MW 149), the putatively toxic acetaminophen metabolite, from the PFB ether derivative of NAPAP. GC-ECNICI-MS of non-derivatized NAPAP did not produce NAPQI. The peak area ratio of m/z 149 to m/z 150 and of m/z 153 to m/z 154 decreased with increasing ion-source temperature in the range 100-250°C. Most likely, NAPQI formed in the ion-source captures secondary electrons to become negatively charged (i.e., [NAPQI](-)) and thus detectable. Formation of NAPQI was not observed under electron ionization (EI) conditions, i.e., by GC-EI-MS, from derivatized and non-derivatized NAPAP. NAPQI was not detectable in flow injection analysis LC-MS of native NAPAP in positive electrospray ionization (ESI) mode, whereas in negative ESI mode low extent NAPQI formation was observed (<5%). Our results suggest that oxidation of drug derivatives in the ion-sources of mass spectrometers may form intermediates that are produced from activated drugs in enzyme-catalyzed reactions.
    MeSH term(s) Acetaminophen/chemistry ; Acetonitriles ; Analgesics, Non-Narcotic/chemistry ; Benzoquinones/chemistry ; Fluorobenzenes/chemistry ; Gas Chromatography-Mass Spectrometry/methods ; Imines/chemistry ; Methane
    Chemical Substances Acetonitriles ; Analgesics, Non-Narcotic ; Benzoquinones ; Fluorobenzenes ; Imines ; pentafluorobenzyl bromide (1765-40-8) ; Acetaminophen (362O9ITL9D) ; N-acetyl-4-benzoquinoneimine (G6S9BN13TI) ; Methane (OP0UW79H66) ; acetonitrile (Z072SB282N)
    Language English
    Publishing date 2011-05-15
    Publishing country Netherlands
    Document type Journal Article
    ZDB-ID 1180823-8
    ISSN 1873-376X ; 0378-4347 ; 1570-0232 ; 1387-2273
    ISSN (online) 1873-376X
    ISSN 0378-4347 ; 1570-0232 ; 1387-2273
    DOI 10.1016/j.jchromb.2011.01.025
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  10. Article ; Online: Development, validation and biomedical applications of stable-isotope dilution GC-MS and GC-MS/MS techniques for circulating malondialdehyde (MDA) after pentafluorobenzyl bromide derivatization: MDA as a biomarker of oxidative stress and its relation to 15(S)-8-iso-prostaglandin F2α and nitric oxide (NO).

    Tsikas, Dimitrios / Rothmann, Sabine / Schneider, Jessica Y / Suchy, Maria-Theresia / Trettin, Arne / Modun, Darko / Stuke, Nadine / Maassen, Norbert / Frölich, Jürgen C

    Journal of chromatography. B, Analytical technologies in the biomedical and life sciences

    2016  Volume 1019, Page(s) 95–111

    Abstract: Malondialdehyde (MDA, CH2(CHO)2) is one of the best investigated and most frequently measured biomarkers of lipid peroxidation in biological fluids, a constituent of the so called thiobarbituric acid reactive substances (TBARS). The reaction of ... ...

    Abstract Malondialdehyde (MDA, CH2(CHO)2) is one of the best investigated and most frequently measured biomarkers of lipid peroxidation in biological fluids, a constituent of the so called thiobarbituric acid reactive substances (TBARS). The reaction of thiobarbituric acid with MDA and other carbonyl compounds is the basis for the batch TBARS assay, one of the most commonly and widely used assays of oxidative stress. Yet, the TBARS assay lacks specificity even if combined with HPLC separation prior to visible absorbance or fluorescence detection. In this article, we report highly specific and sensitive stable-isotope dilution GC-MS and GC-MS/MS methods for the quantitative determination of MDA in human plasma (0.1 mL). These methods utilize the acidity (pKa, 4.46) of the two methylene H protons of MDA in aqueous solution, which are as acidic as acetic acid. Endogenous MDA in native plasma and the externally added internal standard [1,3-(2)H2]-MDA (d2-MDA, CH2(CDO)2) are derivatized in aqueous acetone (400 μL) with pentafluorobenzyl (PFB) bromide (10 μL). The reaction products were identified as C(PFB)2(CHO)2 (molecular weight, 432) and C(PFB)2(CDO)2) (molecular weight, 434), respectively. After solvent extraction with toluene (1 mL) quantification is performed by selected-ion monitoring (SIM) in GC-MS and by selected-reaction monitoring (SRM) in GC-MS/MS in the electron-capture negative-ion chemical ionization (ECNICI) mode. In the SIM mode, the anions [M-PFB](-) at m/z 251 for MDA and m/z 253 for d2-MDA are detected. In the SRM mode, the mass transitions m/z 251 to m/z 175 for MDA and m/z 253 to m/z 177 for d2-MDA are monitored. The method was thoroughly validated in human plasma. Potential interfering substances including anticoagulants and commercially available monovettes commonly used for blood sampling were tested. The lowest MDA concentrations were measured in serum followed by heparinized and EDTA plasma. The GC-MS and GC-MS/MS methods were found to be specific, precise, accurate and sensitive. Thus, the LOD of the GC-MS/MS method was determined to be 2 amol (2 × 10(-18)mol) MDA. The GC-MS/MS method is exceedingly useful in clinical settings. We report several biomedical applications and discuss the utility of circulating MDA as a biomarker of lipid peroxidation, especially in long-term clinical studies, and its relation to the F2-isoprostane 15(S)-8-iso-prostaglandin F2α and nitric oxide (NO).
    MeSH term(s) Biomarkers/blood ; Biomarkers/urine ; Deuterium/chemistry ; Dinoprost/metabolism ; Fluorobenzenes/chemistry ; Gas Chromatography-Mass Spectrometry/methods ; Humans ; Indicator Dilution Techniques ; Malondialdehyde/blood ; Malondialdehyde/chemistry ; Malondialdehyde/urine ; Nitric Oxide/metabolism ; Oxidative Stress ; Tandem Mass Spectrometry/methods
    Chemical Substances Biomarkers ; Fluorobenzenes ; pentafluorobenzyl bromide (1765-40-8) ; Nitric Oxide (31C4KY9ESH) ; Malondialdehyde (4Y8F71G49Q) ; Deuterium (AR09D82C7G) ; Dinoprost (B7IN85G1HY)
    Language English
    Publishing date 2016-04-15
    Publishing country Netherlands
    Document type Evaluation Studies ; Journal Article
    ZDB-ID 1180823-8
    ISSN 1873-376X ; 0378-4347 ; 1570-0232 ; 1387-2273
    ISSN (online) 1873-376X
    ISSN 0378-4347 ; 1570-0232 ; 1387-2273
    DOI 10.1016/j.jchromb.2015.10.009
    Database MEDical Literature Analysis and Retrieval System OnLINE

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