Chemical electron-transfer reactions in electrospray mass spectrometry: Effective oxidation potentials of electron-transfer reagents in methylene chloride

Journal Article · Sat Oct 15 00:00:00 EDT 1994 · Analytical Chemistry (Washington); (United States)

DOI:https://doi.org/10.1021/ac00092a018· OSTI ID:6835532

Van Berkel, G J; Zhou, F ^[1]

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1. Oak Ridge National Lab., TN (United States)

Cyclic voltammetry (CV), UV/visible absorption spectroscopy, and electrospray mass spectrometry (ES-MS) are used in conjunction to study the mono- and /or dications produced in solution from the reaction of three model compounds ([beta]-carotene, cobalt(II) octaethylporphyrin (Co[sup II]OEP), nickel(II) octaethylporphyrin (Ni[sup II]OEP), in three different solvent/electron-transfer reagent systems (methylene chloride/0.1% trifluoroacetic acid (TFA) (v/v), methylene chloride/0.1% TFA/2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) v/v/200 [mu]M), methylene chloride/0.1% TFA/0.1% antimony pentafluoride (SbF[sub 5]) (v/v/v)). The reactions were carried out on-line with ES-MS by means of flow injection. Correlation of the CV data for these analytes with the ionic species determined to be in the solution on the basis of UV/visible absorption spectra and/or on the basis of the ionic species observed in the gas phase by ES-MS, along with our previously published data on these solvent/reagent systems, allowed an effective oxidation potential range, E, to be assigned to these solvent/reagent systems: methylene chloride/0.1% TFA (v/v), 0.6V [le] E[sub TFA] < 0.7 V; methylene chloride/0.1% TFA/DDQ (v/v/200 [mu]M), 0.8 [le] E[sub TFA/DDQ] < 1.0 V; methylene chloride/0.1% TFA/0.1% SbF[sub 5] (v/v/v), 1.3 [le] E[sub TFA/SbF(5)] < 1.5. 40 refs., 7 figs.

• DOE Contract Number: AC05-84OR21400
• OSTI ID: 6835532
• Journal Information: Analytical Chemistry (Washington); (United States), Vol. 66:20; ISSN 0003-2700
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ORGANIC COMPOUNDS
CHEMICAL REACTIONS
OXIDATION
ORGANOMETALLIC COMPOUNDS
ABSORPTION SPECTRA
CATIONS
COBALT COMPLEXES
ELECTROCHEMISTRY
ELECTRON TRANSFER
MASS SPECTROSCOPY
METHYLENE CHLORIDE
NICKEL COMPLEXES
PORPHYRINS
REDOX REACTIONS
SOLUTIONS
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
VOLTAMETRY
CARBOXYLIC ACIDS
CHARGED PARTICLES
CHEMISTRY
COMPLEXES
DISPERSIONS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
IONS
MIXTURES
ORGANIC ACIDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* - Chemical &amp; Physicochemical Properties
400102 - Chemical &amp; Spectral Procedures