A Role for Electrospray Mass Spectrometry in Electrochemical Studies

Bond, Alan M.; Colton, R.; D’Agostino, Antonella; Downard, Alison J.; Traeger, John C.

doi:10.1021/ac00106a007

Cited by 67 publications

(57 citation statements)

References 15 publications

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“…[7] Cole et al, [8,9] Bond et al, [10] and Van Berkel et al, [11,12] used different configurations of electrochemical cells coupled to on-line ESI mass spectrometers for the investigation of redox reactions. We have devised an on-line concentric electrochemical cell connected to ESI-MS in which the counter-electrode and its products are separated from the reacting stream reaching the ESI-MS in order to isolate and protect the reduced compounds from the oxidized substances generated at the counter-electrode.…”

Section: Introductionmentioning

confidence: 99%

Studies on the Reduction of [(C₅Me₅)₂Mo₂O₅] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry

et al. 2003

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The complex [Cp* 2 Mo 2 O 5 ] (Cp* = η 5 -C 5 Me 5 ) and its electrochemical reduction products in acetic acid/acetate-buffered (pH = 4.0) water/methanol solutions were investigated by combined electrochemical (EC) flowcell and on-line electrospray ionization mass spectrometry (ESI-MS). Mono-, di-, tri-, and tetranuclear organometallic molybdenum oxides were identified in the starting solution. The effect of the relevant ESI-MS parameters (ionic mode, heated capillary voltage, and heated capillary temperature) and of the concentration on the observed distribution of ions in the mass spectrometer was studied in order to minimize side reactions in the ESI chamber. It was verified that reduction in the ESI-MS is

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Section: Introductionmentioning

confidence: 99%

Studies on the Reduction of [(C₅Me₅)₂Mo₂O₅] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry

et al. 2003

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“…Bond and co-workers [20] used a simple EC system comprised of two tubular platinum electrodes coupled with ES-MS to investigate the anodic electrolysis of metal-diethyldithiocarbamate complexes. Our group has reported the coupling of three different types of cells on line with ES-MS, viz., a two electrode tubular¯ow through cell, a commercially available thin-layer ow-by electrode cell, and a commercially available porous electrode¯ow through cell [21,22].…”

Section: Introductionmentioning

confidence: 99%

A Thin-Layer Electrochemical Flow Cell Coupled On-Line with Electrospray-Mass Spectrometry for the Study of Biological Redox Reactions

Deng

Berkel²

1999

Electroanalysis

107

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A three electrode thin-layer,¯ow-by electrode cell was coupled on-line with electrospray-mass spectrometry (i.e., ECaES-MS) for the study of biological redox reactions. The cell made use of a commercially available 6.0 mm diameter, offset glassy carbon disk working electrode, a AgaAgCl reference electrode, and a workingacounter electrode spacing gasket (16 mm), along with a home-built PEEK counter electrode block with a Pt foil (7.0 mm wide) counter electrode (cell volume ca. 1.1 mL). Off-line hydrodynamic voltammetry experiments and electrolytic conversion ef®ciency measurements using chronocoulometry were used to characterize the performance of the cell. On-line ECaES-MS conversion ef®ciency was found consistent with the off-line results and the ECaES-MS response time was measured as 5.1 s at a¯ow rate of 30 mLamin and 2.4 s at 62 mLamin. The use of this hybrid system for the study of the products of biologically relevant redox reactions was demonstrated using the oxidation of dopamine in aqueous CH 3 OH (pH 4.0) as a test case. Tandem mass spectrometry experiments provided evidence to conclude that the structure of the two major dopamine oxidation products observed in the ES mass spectra were 5,6-dihydroxyindoline and 5,6-hydroxyindole. Reaction of oxidized dopamine with the surrogate biogenic nucleophile benzene thiol resulted in the formation of mono-, di-, and tri-benzene thiol addition products. These spectra also indicated that the reaction of oxidized dopamine with benzene thiol was signi®cantly faster than the intermolecular cyclization reaction of this intermediate, which normally produces 5,6-dihydroxyindoline.

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“…In several articles hyphenation of a thin-layer electrochemical cell with thermospray MS [111] and particle beam MS [112] was shown. Electrochemical system with two tubular Pt electrodes coupled with electrospray MS was used to study the anodic oxidation of metal-diethyldithiocarbamate complexes [113]. A commercially available electrochemical flow cell was used in biological application with electrospray MS as reactor before the HPLC column to study tryptophan metabolites [114].…”

Section: Hyphenated Electroanalytical Flow Methodsmentioning

confidence: 99%

Electroanalytical Flow Measurements–Recent Advances

2003

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As general trends in current development of chemical analysis, including electroanalysis, one can indicate a search for methods fast and multianalyte, for miniaturized measuring devices, mechanization and automation of analytical processes. In all these trends a significant role is played by measurements in flow conditions. The major advantage of flow electroanalysis is a possibility of utilizing a kinetic discrimination in potentiometric measurements and enhancement of mass transport in voltammetric techniques. Flow injection techniques provide shortening of time of a single analytical determination due to reproducible use of transient signal from the detector without need of obtaining a steady-state equilibrium signal. Electrochemical detection in HPLC gives often improved selectivity and detection limit for electroactive solutes, whereas in capillary electrophoresis it allows a convenient design of portable, integrated chips for field application. This review presents state-of-the -art of flow electroanalysis based on 226 cited literature references

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A Role for Electrospray Mass Spectrometry in Electrochemical Studies

Cited by 67 publications

References 15 publications

Studies on the Reduction of [(C₅Me₅)₂Mo₂O₅] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry

Studies on the Reduction of [(C₅Me₅)₂Mo₂O₅] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry

A Thin-Layer Electrochemical Flow Cell Coupled On-Line with Electrospray-Mass Spectrometry for the Study of Biological Redox Reactions

Electroanalytical Flow Measurements–Recent Advances

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A Role for Electrospray Mass Spectrometry in Electrochemical Studies

Cited by 67 publications

References 15 publications

Studies on the Reduction of [(C5Me5)2Mo2O5] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry

Studies on the Reduction of [(C5Me5)2Mo2O5] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry

A Thin-Layer Electrochemical Flow Cell Coupled On-Line with Electrospray-Mass Spectrometry for the Study of Biological Redox Reactions

Electroanalytical Flow Measurements–Recent Advances

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Studies on the Reduction of [(C₅Me₅)₂Mo₂O₅] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry

Studies on the Reduction of [(C₅Me₅)₂Mo₂O₅] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry