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Eur. J. Mass Spectrom. 12, 1–14 (2006)
DOI: 10.1255/ejms.785

Derivatization in mass spectrometry – 7. On-line derivatisation/degradation

John M. Halket
Drug Control Centre, King’s College London, Franklin-Wilkins Building, Stamford Street, London SE1 9NH, UK. E-mail: john.halket@kcl.ac.uk
Vladimir G. Zaikin
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky prospect 29, 119991 Moscow, Russia. E-mail: zaikin@ips.ac.ru

ABSTRACT:
The review describes on-line derivatization/degradation methods employed in mass spectrometry to solve some structural and analytical problems. Advantages and applications of various positions of reaction systems connected mainly to a mass spectrometer or a gas chromatograph/mass spectrometer are considered. Among these are reaction systems connected directly to the mass spectrometer (reaction mass spectrometry, pyrolysis-mass spectrometry or direct pyrolysis-mass spectrometry); flash-heaters as reactors in gas chromatography/mass spectrometry (GC/MS); in-line chemical reactors located before the chromatographic column [pre-column derivatization/degradation with the use of catalytic reactions, pyrolysis (pyrolysis-GC/MS), degradation in elemental analyzers-isotope ratio mass spectrometry (EA-IRMS)]; on-column derivatization and deuteration; reactor located between the chromatographic column and a mass spectrometer [post-column catalytic derivatization, gas chromatograph-combustion-isotope ratio mass spectrometer (GC-c-IRMS)]. Post-column derivatization in high performance liquid chromatography/mass spectro­metry is briefly mentioned. Application of such on-line methodology to structure elucidation of low molecular mass compounds and polymers, to the determination of isotope ratios of the most common elements, to the investigation of catalytic reactions is discussed..

Keywords: pre-column derivatization, post-column derivatization, on-column derivatization, in-flash heater derivatization, Py-MS, DPMS, Py-GC/MS, polymers, unsaturated compounds, deuteration, oxidation, silylation, acylation, esterification, tetraalkylammonium hydroxides, thermal hydrolytic alkylation, GC-c-IRMS, EA-IRMS, HPLC/MS, isotopic analysis, pyrolyzers, microreactor, hydrogenation, hydrogenolysis, dehydrogenation, hydrodesulpfurization, catalytic reactions

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