The Electrified Liquid‐Liquid Interface

Dryfe, Robert A. W.

doi:10.1002/9780470431917.ch4

Cited by 51 publications

(50 citation statements)

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“…Understanding electron transfer (ET) at the interface between two immiscible electrolyte solutions (IES) is of fundamental importance in electrochemistry, [1][2][3][4][5][6][7] solar energy conversion and "artificial photosynthesis," [8][9] and phase transfer catalysis, [10][11][12] and may also be relevant to understanding biological processes at membrane interfaces and in DNA environments. 13 The experimental study of ET at IES has a long history, 2 but up until recently, measurements of electron transfer rates have mainly utilized conventional electrochemical methods, where the interface was under potentiostatic control.…”

Section: Introductionmentioning

confidence: 99%

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Photoinduced Excited State Electron Transfer at Liquid/Liquid Interfaces

Cooper

Benjamin

2014

J. Phys. Chem. B

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Abstract:Several aspects of the photoinduced electron transfer (ET) reaction between coumarin 314 (C314) and N,N-dimethylaniline (DMA) at the water/DMA interface are investigated by molecular dynamics simulations. New DMA and water/DMA potential energy surfaces are developed and used to characterize the neat water/DMA interface.The adsorption free energy, the rotational dynamics and the solvation dynamics of C314 at the liquid/liquid interface are investigated and are generally in reasonable agreement with available experimental data. The solvent free energy curves for the ET reaction between excited C314 and DMA molecules are calculated and compared with those calculated for a simple point charge model of the solute. It is found that the reorganization free energy is very small when the full molecular description of the solute is taken into account. An estimate of the ET rate constant is in reasonable agreement with experiment. Our calculations suggest that the polarity of the surface "reported" by the solute, as reflected by solvation dynamics and the reorganization free energy, is strongly solute-dependent.

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Section: Introductionmentioning

confidence: 99%

“…This includes scanning electrochemical microscopy (SECM), [15][16][17][18][19][20][21][22][23][24][25][26] thin-layer cyclic voltammetry, [27][28] and spectro-electrochemical methods (some utilizing recent advances in non-linear optics). [5][6][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] 3…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Excited State Electron Transfer at Liquid/Liquid Interfaces

Cooper

Benjamin

2014

J. Phys. Chem. B

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“…For many years, the structure and properties of these interfaces have been examined 3,4 and the kinetics and mechanisms 4,5 of ion transfer reactions have been studied. The information emerging from these studies provides a foundation for applications such as the design of membranes, extraction processes, sensors, molecular separations, drug delivery and various other areas.…”

Section: Introductionmentioning

confidence: 99%

“…Several reviews on broader aspects of electrochemistry at the ITIES have been published recently, to which interested readers are referred. [1][2][3][4][5][6] This report is targeted towards analytical 7 and mechanistic information on protein and polypeptide behaviour at the ITIES.…”

Section: Introductionmentioning

confidence: 99%

Voltammetry of proteins at liquid–liquid interfaces

Arrigan

2013

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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“…Most publications have reported mainly the experimental results as summarized in reviews, (11 -13) and in comparison, few theoretical models of charge-transfer processes and the interfacial structure have been proposed, as described in the recent reviews by Dryfe (14) and Samec. (15) Although the potential distribution at the ITIES is now well established, (16) the structure of the interface and the kinetics of transfer are still controversial subjects.…”

Section: Introductionmentioning

confidence: 99%

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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The Electrified Liquid‐Liquid Interface

Cited by 51 publications

References 201 publications

Photoinduced Excited State Electron Transfer at Liquid/Liquid Interfaces

Photoinduced Excited State Electron Transfer at Liquid/Liquid Interfaces

Voltammetry of proteins at liquid–liquid interfaces

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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