A few key theoretical issues of importance in modern molecular electrochemistry

International audienceThis opinion paper details three typical cases in which new theoretical concepts need to be implemented in molecular electrochemistry in order to rationalize experimental results obtained in nanoscale cells or performed in new electrolytic media such as RTILs

Electron Transfer Catalysis of The Hydrogenolysis of Acyl Dicarbonyl Cyclopentadienyliron Complexes by Tributyltin Hydride

The conversion of acyl dicarbonyl cyclopentadienyliron compounds Cp(CO)2Fe(COR) into aldehydes is not straightforward. It is shown here, mainly from electrochemical results, that the hydrogenolysis of the metal acyl bond can be efficiently achieved by trialkytin hydrides under very mild conditions, according to a chain reaction process initiated by an electron transfer to the acyl complex. The expected aldehyde is formed together with the heterobinuclear iron-tin complex

Electron Transfer Catalysis of The Hydrogenolysis of Acyl Dicarbonyl Cyclopentadienyliron Complexes by Tributyltin Hydride

The conversion of acyl dicarbonyl cyclopentadienyliron compounds Cp(CO)2Fe(COR) into aldehydes is not straightforward. It is shown here, mainly from electrochemical results, that the hydrogenolysis of the metal acyl bond can be efficiently achieved by trialkytin hydrides under very mild conditions, according to a chain reaction process initiated by an electron transfer to the acyl complex. The expected aldehyde is formed together with the heterobinuclear iron-tin complex

Theoretical concepts underlying ECL generation

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Electrochemical attachment of a conjugated amino-ferrocifen complex onto carbon and metal surfaces

International audienceThe attachment of a pi-conjugated amino-ferrocifen complex was electrochemically achieved either by direct oxidation of the amino group or via the oxidation of the ferrocene moiety. In the first case, the modification consists in oxidizing, at +0.70V/SCE, the amino moiety to its radical cation, which upon deprotonation from the amino group, yields all aminyl radical that may add onto the electrode surface. Alternatively, it is demonstrated that the amine moiety can be indirectly oxidized through an intramolecular electron transfer from the amino moiety to the ferrocenyl group after oxidation of the ferrocene part at +0.40 V. This can occur thanks to the conjugated pi system of the complex. More importantly. it is demonstrated that the covalent attachment of the complex can be achieved on glassy carbon, gold, and platinum surfaces whatever the approach used. The possible mechanisms for the covalent attachment are discussed. Interestingly, it is also shown that the amino-ferrocene compound adsorbs very well likely via pi stacking between grafted and non-grafted molecules. Nevertheless, the adsorbed molecules could be easily removed after passing the electrode in an ultrasonic bath. The electrode coverage was determined under various conditions by integration of the corresponding voltammograms. (C) 2008 Elsevier B.V. All rights reserved

Theory and computational study of electrophoretic ion separation and focusing in microfluidic channels

In this work we describe the theory and 2D simulation of ion separation and focusing in a new concept of microfluidic separation device. The principle of the method of ion focusing is classical in the sense that it consists in opposing a hydrodynamic transport ensured by the solution flow to an electrophoretic driving force so that any ionic sample results poised within the microchannel at the point where the two forces equilibrate. The originality of the concept investigated here relies on the fact that thanks to the use of an ion-conducting membrane of variable thickness in electrical contact with the channel the electrophoretic force is varied continuously all along the channel length. Similarly, changing the geometric shape of the membrane allows a facile optimization of the device separation and focusing properties

A [3]Ferrocenophane polyphenol showing a remarkable antiproliferative activity on breast and prostate cancer cell lines

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