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Advanced Separation Techniques Combined with Mass Spectrometry for Difficult Analytical Tasks - Isomer Separation and Oil Analysis

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Advanced Separation Techniques Combined with Mass Spectrometry for Difficult Analytical Tasks - Isomer Separation and Oil Analysis FINNISH METEOROLOGICAL INSTITUTE Erik Palménin aukio 1 P.O. Box 503 FI-00101 HELSINKI 131 CONTRIBUTIONS tel. +358 29 539 1000 WWW.FMI.FI FINNISH METEOROLOGICAL INSTITUTE CONTRIBUTIONS No. 131 ISBN 978-952-336-016-7 (paperback) ISSN 0782-6117 Erweko Helsinki 2017 ISBN 978-952-336-017-4 (pdf) Helsinki 2017 ADVANCED SEPARATION TECHNIQUES COMBINED WITH MASS SPECTROMETRY FOR DIFFICULT ANALYTICAL TASKS - ISOMER SEPARATION AND OIL ANALYSIS JAAKKO LAAKIA Department of Chemistry University of Helsinki Finland Advanced separation techniques combined with mass spectrometry for difficult analytical tasks – isomer separation and oil analysis Jaakko Laakia Academic Dissertation To be presented, with the permission of the Faculty of Science of the University of Helsinki, for public criticism in Auditorium A129 of the Department of Chemistry (A.I. Virtasen aukio 1, Helsinki) on May 12th, 2017, at 12 o’clock noon. Helsinki 2017 1 TABLE OF CONTENTS ABSTRACT 4 Supervisors Professor Tapio Kotiaho TIIVISTELMÄ 5 Department of Chemistry LIST OF ORIGINAL PAPERS 6 Faculty of Science ACKNOWLEDGEMENTS 7 ABBREVIATIONS 8 and 1. INTRODUCTION 10 Division of Pharmaceutical Chemistry and Technology 1.1.1 Basic operation principles of ion mobility 12 spectrometry 11 Faculty of Pharmacy 1.1.2 Applications of ion mobility spectrometry 16 University of Helsinki 1.2 Basic operation principles and applications of two-dimensional gas 19 chromatography – time-of-flight mass spectrometry Docent Tiina Kauppila 1.3 Aims of study 23 Division of Pharmaceutical Chemistry and Technology Faculty of Pharmacy 2. EXPERIMENTAL 24 University of Helsinki 2.1 Chemicals 24 2.2 Oil fractioning (Paper IV-V) 27 Reviewers Professor Janne Jänis 2.3 Separation of n-alkanes from branched and cyclic saturated 27 Department of Chemistry hydrocarbons by urea adduct formation (Papers IV-V) Faculty Science and Forestry 2.4 Ion mobility spectrometry instrumentation (Papers I-III) 29 University of Eastern Finland 2.5 Temperature of ion mobility drift tube (Paper I) 31 2.6 Two-dimensional gas chromatography – time-of-flight mass 32 Docent Velimatti Ollilainen spectrometry instrumentation (Papers IV-V) Department of Food and Environmental Sciences 2.7 Principle component analysis (Papers IV-V) 33 Faculty of Agriculture and Forestry University of Helsinki 3. RESULTS AND DISCUSSIONS 34 3.1 Sterically hindered phenols (Paper I) 34 Opponent Professor Wolfgang Schrader 3.2 Separation of different ion structures (Paper II) 38 Max-Planck-Institut für Kohlenforschung 3.3 Separation of isomers 41 Mülheim an der Ruhr, Germany 3.4 Geochemistry of Recôncavo Basin, Brazil, oils (Paper IV) 46 3.5 Geochemistry and identification of compounds in Brazilian 53 Custos Professor Marja-Liisa Riekkola crude oils (Paper V) Department of Chemistry 4. CONCLUSIONS 63 University of Helsinki REFERENCES 66 PUBLICATIONS I, II, III, IV and V 77 ISBN 978-952-336-016-7 (Paperback) ISSN 0782-6117 Erweko Oy Helsinki 2017 ISBN 978-952-336-017-4 (PDF) http://ethesis.helsinki.fi Helsingin yliopiston verkkojulkaisut 2 3 TABLE OF CONTENTS ABSTRACT 4 Supervisors Professor Tapio Kotiaho TIIVISTELMÄ 5 Department of Chemistry LIST OF ORIGINAL PAPERS 6 Faculty of Science ACKNOWLEDGEMENTS 7 ABBREVIATIONS 8 and 1. INTRODUCTION 10 Division of Pharmaceutical Chemistry and Technology 1.1.1 Basic operation principles of ion mobility 12 spectrometry 11 Faculty of Pharmacy 1.1.2 Applications of ion mobility spectrometry 16 University of Helsinki 1.2 Basic operation principles and applications of two-dimensional gas 19 chromatography – time-of-flight mass spectrometry Docent Tiina Kauppila 1.3 Aims of study 23 Division of Pharmaceutical Chemistry and Technology Faculty of Pharmacy 2. EXPERIMENTAL 24 University of Helsinki 2.1 Chemicals 24 2.2 Oil fractioning (Paper IV-V) 27 Reviewers Professor Janne Jänis 2.3 Separation of n-alkanes from branched and cyclic saturated 27 Department of Chemistry hydrocarbons by urea adduct formation (Papers IV-V) Faculty Science and Forestry 2.4 Ion mobility spectrometry instrumentation (Papers I-III) 29 University of Eastern Finland 2.5 Temperature of ion mobility drift tube (Paper I) 31 2.6 Two-dimensional gas chromatography – time-of-flight mass 32 Docent Velimatti Ollilainen spectrometry instrumentation (Papers IV-V) Department of Food and Environmental Sciences 2.7 Principle component analysis (Papers IV-V) 33 Faculty of Agriculture and Forestry University of Helsinki 3. RESULTS AND DISCUSSIONS 34 3.1 Sterically hindered phenols (Paper I) 34 Opponent Professor Wolfgang Schrader 3.2 Separation of different ion structures (Paper II) 38 Max-Planck-Institut für Kohlenforschung 3.3 Separation of isomers 41 Mülheim an der Ruhr, Germany 3.4 Geochemistry of Recôncavo Basin, Brazil, oils (Paper IV) 46 3.5 Geochemistry and identification of compounds in Brazilian 53 Custos Professor Marja-Liisa Riekkola crude oils (Paper V) Department of Chemistry 4. CONCLUSIONS 63 University of Helsinki REFERENCES 66 PUBLICATIONS I, II, III, IV and V 77 ISBN 978-952-336-016-7 (Paperback) ISSN 0782-6117 Erweko Oy Helsinki 2017 ISBN 978-952-336-017-4 (PDF) http://ethesis.helsinki.fi Helsingin yliopiston verkkojulkaisut 2 3 Julkaisun sarja, numero ja raporttikoodi Finnish Meteorological Institute Series title, number and report code of Contribution 131, FMI-CONT-131 publication Julkaisija Ilmatieteen laitos, ( Erik Palménin aukio 1) Published by Finnish Meteorological Institute Finnish Meteorological Institute PL 503, 00101 Helsinki Julkaisuaika: Toukokuu 2017 (Erik Palménin aukio 1) , P.O. Box 503 Contribution 131, FMI-CONT-131 FIN-00101 Helsinki, Finland Tekijä: Date May 2017 Jaakko Laakia Author: Nimeke Jaakko Laakia Massaspektometriin kytketyt kehittyneet esierotustekniikat vaikeissa analyyttisissa tehtävissä – isomeerien Title: erotuksessa ja öljyanalytiikassa Advanced separation techniques combined with mass spectrometry for difficult analytical tasks – isomer separation Tiivistelmä and oil analysis Abstract Väitöskirja koostuu kahdesta osiosta. Ensimmäisessä osiossa perehdytään ioniliikkuvuusspektrometria– massaspektrometriaan (IMS-MS), jolla tutkittiin ionien liikkuvuutta kaasufaasissa, ja toisessa kaksiulotteiseen This thesis covers two aspects of utilisation of advanced separation technology together with mass kaasukromatografia–massaspektrometriaan (GC×GC-TOF-MS), jolla karakterisoitiin raakaöljynäytteitä. Yksi IMS tutkimuksen tavoitteista oli erotella isomeerejä. Osa tutkituista isomeereistä erottui hyvin ja osa ei. spectrometry: 1. Drift tube ion mobility spectrometry – mass spectrometry (IMS-MS) studies of the Tarkemmassa tarkastelussa huomattiin, että yhdisteiden tietyt funktionaaliset ryhmät pystyvät ”suojaamaan” behaviour of ions in the gas phase and 2. Comprehensive two dimensional gas chromatography – time-of- molekyylin varautunutta funktionaalista ryhmää. Tällä efektillä oli suuri merkitys isomeerien erottumisessa, sillä flight mass spectrometry (GC×GC-TOF-MS) studies for characterization of crude oil samples. esimerkiksi amiinit, joiden varauskohta oli ”suojattu” erottuivat IMS:llä ioneista, joiden varauskohta oli In IMS studies, the focus was on the separation of isomeric compounds. For example, [M-H]- ions of 2,4- ”avoimempi”. Erilaisia addukti-ioneja (analyytin ja pienmolekyylin yhteenliittymä) havaittiin joillekin mitatuille di-tert-butylphenol (2,4-DtBPh) and 2,6-di-tert-butylphenol (2,6-DtBPh) were separated. It was also yhdisteille. Mikäli adduktin muodostus tapahtuu vain toiselle isomeerille niin isomeerit erottuvat IMS:lla esim. 2,4- observed that shielding of the charge site by the functional groups of a molecule has a large effect on the di-tert-butylphenolien (2,4-DtBPh) muodosti [M+O2]-· addukti-ionin ja erottui 2,6-DtBPh-isomeeristä mikä ei separation of the isomeric compounds. For example, amines with a shielded charge site were separated muodostanut vastaavaa addukti-ionia. di-tert-butyilipyridiini taas muodosti [M]+ ja [M+O2]+·ionin. Näille from those with a more open charge site, while some of the isomeric amines studied were not separated. molemmille ioneille mitattiin sama liikkuvuus, mutta se pystyttiin erottamaan saman yhdisteen eri ioni muodosta, [M+H]+, IMS:llä. Tutkimuksessa osoitettiin, että on tärkeää mitata liikkuvuus saman yhdisteen eri ionimuodoille, Different kinds of adduct ions were observed for some of the analytes. Dioxygen adducts were seen for erityisesti dihappiaddukteille, jotta ymmärrettäisiin paremmin ionien muodomismekanismeja sekä adduktien 2,4-DtBPh [M+O2]-, 2,6-di-tert-butylpyridine (2,6-DtBPyr) [M+O2]+· and 2,6-di-tert-butyl-4- vaikutusta eri ionimuotojen ja isomeerien erottumiselle IMS:ssä. methylpyridine (2,6-DtB-4MPyr) [M+O2]+·. The adduct formation increases the total mass of the analyte Väitöskirjan GC×GC-TOF-MS osiossa karakterisoitiin raakaöljynäytteitä. Esimerkiksi Brasilian Recôncavo Basin ion, and therefore, for example the 2,4-DtBPh [M+O2]- ion could be separated from its isomeric öljykentältä kerätyt näytteet voitiin jakaa kahteen ryhmään käyttämällä näytteiden luokitukseen alhaisen pitoisuuden compound 2,6-DtBPh [M-H]-, which did not from the dioxygen adduct ion. In the case of 2,6-DtBPyr and näytekomponentteja. GC×GC-TOF-MS mittaukset osoittivat korrelaation toisen dimensio GC-erotuksen retentioajan 2,6-DtB-4MPyr, the [M]+ ions formed dioxygen adduct [M+O2]+· ions. The both ions, [M]+ and ja tunnettujen saturoituneiden hiilivetyjen renkaiden määrän ja niissä olevien hiiliatomien lukumäärän välillä. Tätä [M+O2]+·, shared the same drift time which was longer
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