Artifacts in Amine Analysis from Anodic Oxidation of Organic Solvents upon Electrospray Ionization for Mass Spectrometry

Different phenylenediamines were used to explore anodic oxidation in solution during electrospray ionization (ESI) mass spectrometry analysis. In our experiments, a series of unknown ionic species was detected in the phenylenediamine solutions. Our results propose that reactions of phenylenediamines with species formed by anodic oxidation of typical ESI solvents during the electrospray ionization process such as formaldehyde are producing these peaks. Identification of these compounds inter alia suggests formal alkylation, a reaction not reported so far as a result of electrolytic oxidation in the prospective organic solvents.

[1]  Cuirong Sun,et al.  Hydride abstraction in positive-ion electrospray interface: oxidation of 1,4-dihydropyridines in electrospray ionization mass spectrometry. , 2011, The Analyst.

[2]  U. Krewer,et al.  Electrochemical oxidation of carbon-containing fuels and their dynamics in low-temperature fuel cells. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[3]  Brandie M. Ehrmann,et al.  Relative importance of basicity in the gas phase and in solution for determining selectivity in electrospray ionization mass spectrometry , 2008, Journal of the American Society for Mass Spectrometry.

[4]  M. Schäfer,et al.  Radical Cations in Electrospray Mass Spectrometry: Formation of Open‐Shell Species, Examination of the Fragmentation Behaviour in ESI‐MSn and Reaction Mechanism Studies by Detection of Transient Radical Cations , 2007 .

[5]  M. C. Granger,et al.  Efficient analyte oxidation in an electrospray ion source using a porous flow-through electrode emitter , 2004, Journal of the American Society for Mass Spectrometry.

[6]  Pier Giorgio Zambonin,et al.  o-Phenylenediamine Electropolymerization by Cyclic Voltammetry Combined with Electrospray Ionization-Ion Trap Mass Spectrometry , 2003 .

[7]  J. Rossier,et al.  On-line electrochemical tagging of cysteines in proteins during nanospray , 2002 .

[8]  R. Hettich,et al.  N‐Phenyl‐1,4‐Phenylenediamine and Benzidine Oxidation Products Identified Using On‐Line Electrochemistry/Electrospray Fourier Transform Mass Spectrometry , 2002 .

[9]  V. Kertész,et al.  Surface-assisted reduction of aniline oligomers, N-phenyl-1,4-phenylenediimine and thionin in atmospheric pressure chemical ionization and atmospheric pressure photoionization , 2002, Journal of the American Society for Mass Spectrometry.

[10]  P. Schnier,et al.  Electrochemical processes in a wire-in-a-capillary bulk-loaded, nano-electrospray emitter , 2001, Journal of the American Society for Mass Spectrometry.

[11]  Quirke,et al.  Derivatization for electrospray ionization-mass spectrometry. 4. Alkenes and alkynes , 2000, Rapid communications in mass spectrometry : RCM.

[12]  James,et al.  Electrochemical Reactions and Mechanisms in Organic Chemistry || Oxidation of Alcohols, Amines and Amides , 2000 .

[13]  N. Lawrence,et al.  Selective determination of thiols: a novel electroanalytical approach , 2000 .

[14]  A. Bard,et al.  Hydroquinone as a buffer additive for suppression of bubbles formed by electrochemical oxidation of the CE buffer at the outlet electrode in capillary electrophoresis/electrospray ionization-mass spectrometry. , 1999, Analytical chemistry.

[15]  C. Korzeniewski,et al.  FORMALDEHYDE YIELDS FROM METHANOL ELECTROCHEMICAL OXIDATION ON PLATINUM , 1998 .

[16]  Feimeng Zhou,et al.  Changes in bulk solution pH caused by the inherent controlled-current electrolytic process of an electrospray ion source , 1997 .

[17]  X. Xia,et al.  Structural effects and reactivity in methanol oxidation on polycrystalline and single crystal platinum , 1996 .

[18]  G. J. Berkel,et al.  Observation of gas-phase molecular dications formed from neutral organics in solution via the controlled-current electrolytic process inherent to electrospray , 1996, Journal of the American Society for Mass Spectrometry.

[19]  L. Radom,et al.  Water-Catalyzed Interconversion of Conventional and Distonic Radical Cations: Methanol and Methyleneoxonium Radical Cations , 1996 .

[20]  G. J. Berkel,et al.  Characterization of an Electrospray Ion Source as a Controlled-Current Electrolytic Cell , 1995 .

[21]  G. Glish,et al.  Electrochemical Origin of Radical Cations Observed in Electrospray Ionization Mass Spectra , 1992 .

[22]  P. Kebarle,et al.  Mechanism of electrospray mass spectrometry. Electrospray as an electrolysis cell , 1991 .

[23]  G. Glish,et al.  Preforming ions in solution via charge-transfer complexation for analysis by electrospray ionization mass spectrometry , 1991 .

[24]  J. Doucet,et al.  In-situ investigation of the film growth mechanism using multiple internal reflection fourier transform infrared spectroscopy (MIRFTIRS) Part I. Behaviour of iron and platinum electrodes in alkaline methanolic solutions , 1986 .

[25]  J. S. Swenton.  Quinone bis- and monoketals via electrochemical oxidation versatile intermediates for organic synthesis , 1983 .

[26]  H. B. Stegmann,et al.  o‐Wurster‐Radikal‐Kationen und ‐Anionen , 1976 .

[27]  A. Bullock,et al.  TEMPERATURE-DEPENDENT HYPERFINE COUPLING CONSTANTS IN ELECTRON SPIN RESONANCE PART 3, AMINO GROUP ROTATION IN THE CATION OF P-PHENYLENEDIAMINE , 1975 .

[28]  A. Bullock,et al.  Temperature-dependent hyperfine coupling constants in electron spin resonance. Part 3.—Amino group rotation in the cation of p-phenylenediamine , 1975 .

[29]  M. Scholz,et al.  MO-Berechnungen zur photographischen Farbentwicklung. I Berechnungen an p-Phenylendiaminen , 1971 .

[30]  N. Weinberg,et al.  Electrochemical oxidation of organic compounds , 1968 .

[31]  V. S. Bagotzky,et al.  Mechanism of electro-oxidation of methanol on the platinum electrode☆ , 1967 .

[32]  R. Norberg,et al.  Measurement of the Rate of an Electron Exchange Reaction by Nuclear Magnetic Resonance Spectroscopy , 1956 .

[33]  C. Wurster,et al.  Zur Kenntniss des Dimethylparaphenylendiamins , 1879 .