Fluoroalcohols as Components of LC-ESI-MS Eluents: Usage and Applications
| dc.contributor.author | Kipper, Karin | |
| dc.date.accessioned | 2012-07-10T19:23:08Z | |
| dc.date.available | 2012-07-10T19:23:08Z | |
| dc.date.issued | 2012-07-10 | |
| dc.description | Väitekirja elektrooniline versioon ei sisalda publikatsioone. | et |
| dc.description.abstract | Ravimite kui peamiselt aluseliste ühendite pöördfaasvedelikkromatograafilised määramismetoodikad on seni kasutanud elueerimist eluendi madalal pH-l, kus analüüdid on protoneeritud ning seetõttu polaarsemad ja omavad viletsat retentsiooni. Analüütide määramiseks pöördfaaskromatograafias kasutatakse laialdaselt massispektromeetrilist detektorit, mis omakorda seab kasutatavatele eluentidele lenduvuse nõude. Aluseliste analüütide retentsiooni parandamiseks vedelikkromatograafilisel-massispektromeetrilisel (LC-MS) analüüsil tuleks kasutada kõrgemat puhverlahuse pH-d. Lenduvate aluseliste puhverlahuste valiku, mis on hetkel üsna piiratud, laiendamiseks uuriti fluoroalkohole - 1,1,1,3,3,3-heksfluoro-2-propanool (pKa=9.3) ja 1,1,1,3,3,3-heksafluoro-2-metüül-2-propanool (pKa=9.6) kasutusvõimalusi LC-MS aluseliste puhverlahustena. Töö tulemusena kirjeldati fluoroalkoholide kasutamisel pöördfaaskromatograafia retentsioonimehhanisme, fluoroalkoholide mõju analüütide ionisatsioonile, võrreldi mõju analüütide retentsioonile kasutades fluoroalkohole ning fluoreeritud statsionaarset faasi ning esitati fluoroalkoholide kasutamise eelised. Võrreldes tavapäraste puhverlahustega pakuvad fluoroalkoholid puhverlahustena analüütidele alternatiivseid retentsioonimehhanisme, mis parandab analüütide kromatograafilist lahutust. Töö käigus demonstreeriti fluoroalkoholide kasutamise edukaid rakendusnäiteid ravimite analüüsil keskkonnaproovidest ning inimese kehavedelikest. | et |
| dc.description.abstract | Reversed phase chromatographyc methods for analysis of pharmaceuticals (as mainly basic compounds) have used acidic conditions where analytes are predominantly on their protonated (hydrophilic) form and therefore have poor retention on stationary phase. Basic conditions for the analysis of basic compounds is more suitable. For detection, often mass spectrometry is used where volatile buffer solutions are required. Selection of volatile basic buffer compounds is limited for liquid chromatography-mass spectrometry (LC-MS) and therefore enhancements in the selection is more than welcomed. Two fluoroalcohols - 1,1,1,3,3,3-hexafluoro-2-propanol (pKa=9.3) and 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol (pKa=9.6) have been studied and evaluated in usage as LC-MS basic buffer components. As a result of present work the retention mechanisms provided by fluoroalcohols have described, the influence of fluoroalcohols for the ionization of analytes have been described, comparison with retention in fluorinated stationary phase have been demonstrated and advantages for usage of fluorinated alcohols as LC-MS buffer components have been demonstrated. Comparing with known buffer components fluoroalcohols provide alternative retention mechanisms and therefore the chromatographic separation can be enhanced. Successful application of usage of fluorinated alcohols have been demonstrated for analysis of pharmaceuticals in environmental samples and human blood plasma and urine samples. | en |
| dc.identifier.isbn | 978–9949–32–059–2 (trükis) | |
| dc.identifier.isbn | 978–9949–32–060–8 (pdf) | |
| dc.identifier.issn | 1406–0299 | |
| dc.identifier.uri | http://hdl.handle.net/10062/26028 | |
| dc.language.iso | en | et |
| dc.relation.ispartofseries | Dissertationes chimicae Universitatis Tartuensis;119 | |
| dc.subject | farmatseutiline keemia | et |
| dc.subject | fluoriühendid | et |
| dc.subject | alkoholid | et |
| dc.subject | pöördfaasvedelikukromatograafia | et |
| dc.subject | pharmaceutical chemistry | en |
| dc.subject | fluorine compounds | en |
| dc.subject | alcohols | en |
| dc.subject | reversed-phase liquid chromatography | en |
| dc.subject.other | dissertatsioonid | et |
| dc.subject.other | ETD | en |
| dc.subject.other | dissertation | en |
| dc.subject.other | väitekiri | et |
| dc.title | Fluoroalcohols as Components of LC-ESI-MS Eluents: Usage and Applications | en |
| dc.title.alternative | Fluoroalkoholid LC-ESI-MS eluendi komponendina: kasutatavus ja rakendused | et |
| dc.type | Thesis | en |