Biphasic Electrospray Ionization for the Study of Interfacial Complexes

Prudent, Michel; Méndez, Manuel A.

doi:10.2116/analsci.24.1399

Cited by 17 publications

(25 citation statements)

References 50 publications

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“…In addition, this electrochemical oxidation has been observed in thioether crowns. 47 Transition metal ions catalyze the cysteine oxidation by generating reactive intermediates such as radicals. 9,10 Copper plays the role of electron carrier from thiol to oxygen where the complexation of copper(II) is the first step in the oxidation process.…”

Section: Kctcca Reactions With Zn 2+ and Other Reactionsmentioning

confidence: 99%

The role of copper in cysteine oxidation: study of intra- and inter-molecular reactions in mass spectrometry

Prudent

Girault

2009

Metallomics

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Cysteine-containing peptide oxidation was studied both by using an inert platinum electrode and a sacrificial electrode (copper or zinc) generating metallic ions in electrospray ionization mass spectrometry (ESI-MS). Using peptides containing one, two and three cysteines, we have compared the different chemical and electrochemical oxidation pathways of cysteine (RS ÀII H) to cystine (RS ÀI S ÀI R) and to sulfenic, sulfinic and sulfonic acid (RS 0 OH, RS II O 2 H and RS IV O 3 H, respectively). In the absence of copper ions, intra-molecular reactions were the most abundant, whereas inter-molecular reactions were found to be enhanced by the presence of copper ions. These cations favor the formation of 2 : 1 (peptide : copper) complexes compared to 1 : 1 complexes, thus enhancing the formation of inter-molecular bridges. This study highlights the importance of the position of cysteine inside a peptide during disulfide bridge formation.

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Section: Kctcca Reactions With Zn 2+ and Other Reactionsmentioning

confidence: 99%

The role of copper in cysteine oxidation: study of intra- and inter-molecular reactions in mass spectrometry

Prudent

Girault

2009

Metallomics

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“…[22][23][24] The dual-channel microsprayer (see the Tagging of Phosphopeptides Section) was used with reservoirs stuck on it or in a holder. [25,26] These devices were coupled to an ion trap mass spectrometer. These experimental descriptions give an idea about the setup and more details can be found in the cited literature or in the text.…”

Section: Methodsmentioning

confidence: 99%

“…4). [25] This microchip was fixed in a holder connected to a syringe pump that was able to hold two syringes to introduce two different solutions, e.g. water and 1,2-dichloroethane (DCE).…”

Section: Biphasic Esi: Study Of Interfacial Complexationmentioning

confidence: 99%

“…[25] Complexes between the ligand and the ion were observed such as [HTCO-Pb II Cl] + . The formation of 1:1 (ligand to metal) and 2:1 complexes were also achieved with TTCD.…”

Section: Biphasic Esi: Study Of Interfacial Complexationmentioning

confidence: 99%

“…the adsorption and/or extraction of ion pairs, and the complex formation and adsorption at the interface. [25] In addition, the intense mixing within the Taylor cone region should produce several interfaces, and droplets containing the two phases might be formed, the most probable one being an aqueous droplet covered by an organic solvent shell.…”

Section: Biphasic Esi: Study Of Interfacial Complexationmentioning

confidence: 99%

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About the Electrospray Ionization Source in Mass Spectrometry: Electrochemistry and On-chip Reactions

Prudent¹,

Méndez²,

Roussel³

et al. 2009

Chimia

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The present work shows that the electrochemical properties of electrospray ionization (ESI) can be used to add functions to the process. As example, we show how the choice of the electrode material can be used to study interactions between metal ions and biomolecules in mass spectrometry (MS). In positive ionization MS, an electrospray device acts as anode, which implies oxidation reactions. Sacrificial electrodes (made of copper or zinc) are used to supply the electrospray current and to produce cations that are able to react on-line with compounds of interest. Thus, the interactions between copper ions and ligands or peptides were investigated by using a copper electrode. Another example is the in situ electrogeneration of a dinuclear zinc(II) complex for the mass tagging of phosphopeptides when working with a zinc electrode. In order to perform these reactions on the same microchip, a dual-channel microsprayer was used, where one channel was dedicated to the tag electrogeneration and the other to the infusion of a phosphopeptides solution. Finally, this dual-channel microsprayer was used to study complexation at liquid-liquid interfaces in biphasic ESI-MS, such as thioether crowns and lead ions or peptides and phospholipids complexes. These examples illustrate the use of electrochemistry and on-chip reactions in ESI-MS analysis.

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Liquid/Liquid Interfaces, Electrochemistry atUpdate based on the original article by Frédéric Reymond, Hubert H. Girault,Encyclopedia of Analytical Chemistry, © 2000, John Wiley & Sons, Ltd

Peljo

Girault

2012

Encyclopedia of Analytical Chemistry

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This article outlines the electrochemical methodology at the interface between two immiscible electrolyte solutions (ITIES). The fundamental concepts of the thermodynamics in biphasic systems are presented in order to show how ions are distributed between the two adjacent phases and hence, how a Galvani potential difference is established at an ITIES. Polarizable and nonpolarizable ITIES are then characterized, and it is further evidenced that the classical electroanalytical methodology at a solid electrode can be directly transposed to the ITIES, thereby allowing reversible charge‐transfer reactions to be easily monitored and interpreted. This theoretical approach is completed by a review of the analytical methods used at ITIES, namely cyclic voltammetry (CV), hydrodynamic methods, spectroscopic techniques, and micro‐ and nanointerfaces (which are the biphasic analogs of micro‐ and nanoelectrodes). The last part deals with the practical applications that electrochemistry at ITIES has attracted during the past decades in the development of amperometric and coulometric ion sensors and detectors, detection of macromolecules, extraction of metal ions by interfacial formation of a complex, and assessment of the properties and lipophilicity of ionizable drugs.

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Biphasic Electrospray Ionization for the Study of Interfacial Complexes

Cited by 17 publications

References 50 publications

The role of copper in cysteine oxidation: study of intra- and inter-molecular reactions in mass spectrometry

The role of copper in cysteine oxidation: study of intra- and inter-molecular reactions in mass spectrometry

About the Electrospray Ionization Source in Mass Spectrometry: Electrochemistry and On-chip Reactions

Liquid/Liquid Interfaces, Electrochemistry atUpdate based on the original article by Frédéric Reymond, Hubert H. Girault,Encyclopedia of Analytical Chemistry, © 2000, John Wiley & Sons, Ltd

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