This review provides an overview of traceability studies performed to date (April 2009) for olive oils. Special emphasis has been made on the botanical origin because high-quality monovarietal olive oils have been recently introduced on the markets and their quality control requires the development of new and powerful analytical tools as well as new regulations to avoid fraud to consumers. Several parameters with discriminant power have been used for olive oil traceability according to the olive variety used in the production of the oil. They have been considered as traceability markers to the botanical origin and classified, in this work, as compositional and genetical markers.

Coupling of capillary electrophoresis to electrospray mass spectrometry still remains challenging and a topic of research to find the best interface regarding sensitivity, robustness, and ease of use. Here, a nanoflow sheath liquid interface for CE-ESI-MS is presented and compared to both a standard triple-tube sheath liquid and a porous-tip sheathless interface for three groups of analytes. The nanoflow sheath liquid interface with a separation capillary inserted into a glass emitter was initially characterized to facilitate optimization and method development. Implementation of a shut-off valve, syringe pump, and inline filter enabled easy handling and fast analyses, repeatable both in positive and negative modes (intra-day RSD of 6.6 to 12.0%). The same setup was used for sheathless interfacing by exchanging the emitter and using a porous etched tip separation capillary. Both nanoflow interfaces showed similar performance. Average peak areas using the nanoflow sheath liquid interface were a factor of 38 for 6 organic acids in negative mode, 114 and 36 for the light and heavy chain of a monoclonal antibody, and 13 higher for peptides in positive mode compared to the triple-tube interface. This first direct comparison of the three most common interfaces exhibits a strong improvement in sensitivity to the same extent for both nanoflow interfaces, where sheath liquid interfaces offer full flexibility in method development.

A nonaqueous capillary electrophoresis method with electrospray-mass spectrometric detection was developed to study the glycerophospholipid fraction in olive fruit and olive oil samples. In olive fruits, where the information available about the phospholipid fraction was very scarce, results obtained in this work allowed us to complete and improve this knowledge. The glycerophospholipid fraction of the olive fruit samples analyzed was composed of phosphatidylcholine (PC), phosphatidylethanolamine (PE), lysophosphatidylethanolamine (lyso-PE), phosphatidylinositol (PI), phosphatidic acid (PA), lysophosphatidic acid (lyso-PA), and phosphatidylglycerol (PG). Differences in the relative abundance of the glycerophospholipid classes determined were observed as a function of the botanical and geographical origin of the olive fruits analyzed. Interestingly, the olive stone and pulp analyzed also showed different glycerophospholipid compositions. For olive oil, five glycerophospholipids (lyso-PA, PC, PE, lyso-PE, and PG) were detected. Finally, identification of the main molecular species in the different glycerophospholipid classes for the olive fruit samples analyzed was accomplished by tandem mass spectrometric experiments and information from the literature.

Imaged capillary isoelectric focusing (iCIEF) is a powerful separation technique applied frequently for the analysis of biotherapeutics. However, direct mass spectrometric characterization is usually not possible. Here, focused peaks from an iCIEF system are transferred to a four-port nanoliter valve where peaks of interest are cut and transferred directly (flow injection) or via capillary zone electrophoresis to electrospray mass spectrometry. At first, flow injection coupling was tested with a mixture of peptides showing intraday precision (RSD) of 20.0 and 3.4% in area and 15.2 and 6.3% in intensity for angiotensin I and leucine-enkephalin, respectively. For the analysis of charge variants in an intact mAb, flow injection and CZE as second dimension were compared, demonstrating the usability of flow injection even for large proteins. However, improved spectra quality was achieved when CZE-MS was applied. In this way, accurate masses were obtained not only for the main isoform, but also for the main acidic and basic variants. These results demonstrate the power of iCIEF-CZE-MS for the analysis of biotherapeutics.

The potential of the antibiotic vancomycin (VC) as chiral selector for the enantiomeric separation of amino acids by CE-ESI-MS/MS² was investigated for the first time in this work. Derivatization of amino acids with FMOC-Cl was carried out to enable their interaction with VC as well as the formation of precursor ions with larger m/z which were employed in MS² experiments. The partial filling of a coated capillary was employed to avoid the loss in MS sensitivity originated by the introduction of VC in the ionization source. Under optimized conditions, the simultaneous enantiomeric separation and unequivocal identification of 17 amino acids (two of them being nonprotein amino acids) took place in about 20 min with LODs in the micromolar range.