This thesis explores the use of mass spectrometry to define the strengths, and understand solution phase speciation of phenolic oxime-based solvent extractants of the types used in the hydrometallurgical recovery of copper. Chapter 1 reviews briefly the current extraction technology for copper and focuses on hydrometallurgy and the use of phenolic oximes such as 5-nonylsalicylaldoxime. The modification of the latter to improve extraction efficiency is discussed, focussing on the introduction of X-substituents in the 3 position of the benzene ring. Modern mass spectrometry techniques are also discussed with a focus on their application to inorganic systems and their use in achieving the aims of this thesis, as defined above. The work described in chapter 2 involves the development of collision induced dissociation (CID) techniques to determine the relative gas phase stabilities of copper complex anions of the type [Cu(L)(L-H)]-, where LH is a 5-alkyl-3-X-2- hydroxybenzaldehyde oximes and X a range of substituents. The importance of interligand interactions in the outer-coordination sphere and their influence on gas phase anion stability, as defined by CID, is reported. The work described in Chapter 2 on CID is extended in chapter 3 and looks at the effect of charge, of ligand type, LH, and of the nature of the metal on the stability of ionic forms of [M(L)2] complexes, where LH is extended to include 5-alkyl-2- hydroxyphenylethanone oximes. The effects of substitution at the azomethine carbon atom and at the 3-position of the benzene ring and of variation of the nature of the metal on the ion dissociation mechanisms are shown to have a major influence on ion stability under CID conditions. In chapter 4 density functional theory calculations have been used to investigate the influences of substitution at the azomethine carbon atom and at the 3-position of the benzene ring and of variation of the nature of the metal on the gas phase structures of the neutral complexes, [M(L)2]. Gas phase deprotonation and dimerisation enthalpies of the ligands, LH, and enthalpies of formation of [M(L)2] complexes have been calculated and correlates with experimentally determined ligand extraction strength. The ligand type has been extended to include 3-X-2-hydroxybenzaldehyde hydrazones, which have previously been shown to have lower distribution coefficients for copper than the analogous 3-X-substituted oximes. The calculated gas phase formation enthalpies for [M(L)2] show a strong correlation with the strengths as extractants LH, measured as their pH0.5 values for metal uptake. Chapter 5 considers whether mass spectrometry can be used to define the solution equilibria when two different oxime-based ligands, LXH and LYH, compete for Cu(II) in a single phase solution. It has been established that shifts in the relative peak intensities of deprotonated ions derived from the Cu(II) complexes, [Cu(LX)2], [Cu(LY)2] and [Cu(LX)(LY)] reflect changes in the solution composition. The work described in chapter 6 extends the study of solution phase speciation using mass spectrometry. When the Cu(II) and proton concentrations of solutions were varied distinct changes in the resulting electrospray mass spectra were observed and the resulting species were identified using CID and high resolution mass spectrometry. A novel, [Cu3(L-H)3-μ3-O/OH]- species is determined to be a major component of solutions where Cu(II) concentrations are equal to/greater than the LH concentration. Various 3-X-2-hydroxybenzaldehyde oximes (X = CH2NR2) were synthesised. The incorporation of a protonatable arm in the 3-position enabled trinuclear complexes, [Cu3(L-H)3-μ3-OH], to be isolated and fully characterized, including two X-ray determined crystal structures.

Mass spectrometry with electrospray ionization is an excellent method for structural analysis of coordination compounds with outstanding sensitivity and selectivity. However, it fails to detect some low-polar rhenium complexes. This master thesis describes derivatization method of non-ionizable rhenium complexes with 1,2-dihydroxybenzene and 2,3- dihydroxytoluenene. Fragmentation mechanisms and structure of prepared complexes was studied using high resolution mass spectrometry and collision-induced dissociation (CID). Furthermore, density functional theory (DFT) computational method was used for prediction of bond cleavage based on bond lengthening.

Die Systematische Toxikologische Analyse (STA) stellt auf Grund der großen Vielfalt und der ständigen Zunahme an toxikologisch relevanten Substanzen eine der größten Herausforderungen in der chemischen Analyse dar. In der vorliegenden Arbeit wurde daher die Eignung der Flüssigchromatographie in Kombination mit der Hybrid-Quadrupol-Flugzeitmassenspektrometrie (LC-QTOF-MS) für diesen Zweck untersucht. Dazu wurden eine Datenbank mit über 7360 und eine CID-Spektrenbibliothek mit mehr als 2720 toxikologisch relevanten Substanzen erstellt und geeignete Probenvorbereitungsmethoden entwickelt. Die Erprobung der Methoden erfolgte an dotierten Blut- und Haarproben. Hierbei zeigte sich, dass die Analyse im Auto-MS/MS-Modus (Messzyklen von MS- und MS/MS-Spektren) eine Identifizierung basischer Substanzen mittels CID-Spektren zwischen 0,5 und 2 ng/ml im Blut ermöglichte. Die Nachweisgrenzen der für 24 Wirkstoffe validierten Methode in Haaren lagen bei 3 bis 15 pg/mg. Die Eignung der LC-QTOF-MS zur STA von Haarproben wurde an 30 Drogentodesfällen und 60 Todesfällen mit bekannter chronischer Medikamenteneinnahme zu Lebzeiten sowie an 77 Blutproben nachgewiesen. Für die Suche nach Metaboliten wurde ein Metaboliten-Tool entwickelt. In der praktischen Anwendung auf Datenfiles von Blut- und Haarproben erwies sich das Tool als wertvolles Hilfsmittel zur Identifizierung unbekannter Peaks und zur Bestätigung von Suchergebnissen in der Datenbank. Zur automatischen Konzentrationsabschätzung identifizierter Substanzen wurde ein Tool „Estimate Concentration“ geschaffen. Die Überprüfung des Verfahrens an realen Blut- und Haarproben durch Vergleich mit HPLC-DAD- und GC-MS-Ergebnissen wies eine gute Übereinstimmung der Konzentrationen auf. Insgesamt zeigten die Untersuchungen, dass die LC-QTOF-MS zurzeit die am besten geeignete Methode für die STA darstellt. Auch bei einem erst später aufkommenden Verdacht kann eine gezielte Suche in dem bereits gemessenen Datenfile durchgeführt werden. / Due to the large variety and the steady increase of toxicologically relevant substances, systematic toxicological analysis (STA) is one of the most difficult tasks in analytical chemistry and, therefore, a steady topic of research and methodical improvement. For this reason, the suitability of liquid chromatography in combination with hybrid quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) for STA was investigated. For this purpose, a database of more than 7360 and a CID spectra library of more than 2720 toxicologically relevant substances and suitable methods for sample preparation were developed. The application was evaluated at spiked blood and hair samples. It was found that the analysis in Auto-MS/MS mode (alternating measurement cycles of MS and MS/MS spectra) allowed substance identification in blood using CID spectra between 0.5 and 2 ng/ml for basic substances. The detection limits of the validated method in hair ranged from 3 to 15 pg/mg for 24 drugs. The suitability of LC-QTOF-MS for STA was tested for hair samples from 30 drug-related death cases and from 60 death cases with known chronic medication as well as for 77 blood samples. For the search of metabolites, a metabolite tool was developed. In the practical application to data files from blood and hair samples, the tool proved to be very helpful for identification of unknown peaks and for confirmation of results obtained only from the database without CID spectra. A tool "Estimate Concentration" was created for automatic estimation of concentrations of identified substances. The application to real blood and hair samples and the comparison of the concentrations with results from HPLC-DAD and GC-MS showed good agreement. Overall, these investigations showed that LC-QTOF-MS is currently the most favorable method for STA. Because of the comprehensive registration of all substances in a sample, the data files can be checked for the presence of certain poisons even later without new measurements.