Although capillary electrophoresis (CE) coupled to mass spectrometry (MS) is a separation technique not extensively implemented, it offers differential possibilities in the study of polar and ionic metabolites in complex matrices with minimum sample treatment. However, in order to get successful results, some efforts at early stages and following specific recommendations are necessary.In this chapter, we describe our updated and well-tested methods for untargeted metabolomics using CE-MS-TOF for common biological samples: urine, serum or plasma, feces, tissues, and cells. Sample treatment, as well as separation and detection conditions are described in detail and other steps in the workflow for untargeted metabolomics are also explained. Special attention is paid to instrumental setup and advices for daily practice.Characteristic electropherograms obtained with each type of sample are depicted as well as groups of metabolites easily measured by this technique. Their global or individual comparisons have been given undoubtedly important information to unveil altered metabolic pathways, diagnosis, and prognosis or biomarker discovery in the study of diseases or conditions over decades.
Keywords: Biological samples; CE-MS; Fingerprinting; Polar metabolites; Untargeted metabolomics.