Anal. Chem. 2008, 80, 5912–5923
Metabolite Identification Using a Nanoelectrospray LC-EC-array-MS Integrated System Susan Schiavo,† Erika Ebbel,‡ Swati Sharma,§ Wayne Matson,§ Bruce S. Kristal,| Steven Hersch,⊥ and Paul Vouros*,† Barnett Institute and Department of Chemistry and Chemical Biology, Northeastern University, Boston, Massachusetts 02115, Boston University School of Medicine, Albany Street, Boston, Massachusetts 02118, Department of Systems Biochemistry, Bedford VA Medical Center, 200 Springs Road, Bedford, Massachusetts 01430, Department of Neurosurgery, Brigham and Women’s Hospital, 221 Longwood Avenue, LM322B, Boston, Massachusetts 02115, and Department of Neurology, Massachusetts General Hospital, Harvard Medical School, Charlestown, Massachusetts 02108 A novel approach to the parallel coupling of normal-bore high-performance liquid chromatography (LC) with electrochemical-array detection (EC-array) and nanoelectrospray mass spectrometry (MS), based on the use of a nanosplitting interface, is described where both detectors are utilized at their optimal detection mode for parallel configuration. The dual detection platform was shown to maintain full chromatographic integrity with retention times and peak widths at half-height between the EC-array and MS displaying high reproducibility with relative standard deviations of 20 mM buffer) as well as LC flow rate need to be optimized for simultaneous EC-array and MS detection without compromising their respective sensitivities.19 The high-concentration salt buffers typically employed in EC-array analysis are detrimental to ESI-MS analysis, creating analyte adducts and causing ion suppression often rendering analytes of interest undetectable.20 Nanospray-ESI-MS (flow rates
