Spectroscopic studies of molecular interaction at the liquid–liquid interface

Total internal reflection (TIR) spectroscopy is a widely used technique to study soft matter at interfaces. This tutorial review aims to provide researchers with an overview of the principles, experimental design and applications of TIR spectroscopy to enable them to understand how this class of techniques might be used in their research. It also highlights limitations and pitfalls of TIR techniques, which will assist readers in critically analysing the literature. Techniques covered include attenuated total reflection infrared spectroscopy (ATR-IR), TIR fluorescence, TIR Raman scattering and cavity-enhanced techniques. Other related techniques are briefly described.

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“…149 More detail about techniques for the study of liquid-liquid interfaces (not restricted to TIR spectroscopy) can be found in ref. 150 and 151.…”

Section: Adsorption From Solutionmentioning

confidence: 99%

Total internal reflection spectroscopy for studying soft matter

Woods

Bain

2014

Soft Matter

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“…QELS has been used to study the adsorption of aqueous zinc porphyrins and lipids on the liquid-liquid interface, as well as assembly of gold nanoparticles at the interface. (99) A more comprehensive review of the spectroscopic techniques to study liquid/liquid interfaces has been recently published, (109) not only limited to polarized interfaces.…”

Section: Optical Techniquesmentioning

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 reactivity and characterization of interfacial species are generally evaluated by either electrochemical or spectrometric approach. [3][4][5] Some specific features of interfacial species have been reported in terms of molecular assembly and solvation by means of surface-sensitive spectroscopy. [6][7][8] It is known that various surface-active species tend to form their self-aggregates easily at liquid|liquid interfaces in comparison with homogeneous solution systems.…”

Section: Introductionmentioning

confidence: 99%

Potential-Induced Aggregation of Anionic Porphyrins at Liquid|Liquid Interfaces

2017

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The adsorption and self-aggregation of anionic porphyrins were studied at the polarized water|1,2-dichloroethane (DCE) interface by polarization-modulation total internal reflection fluorescence (PM-TIRF) spectroscopy. 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin diacid (HTPPS) and protoporphyrin IX (HPP) exhibited high surface activities at the interface. The selective excitation of interfacial species in PM-TIRF measurements elucidated the potential-induced aggregation mechanism of the porphyrins. The J-aggregates of HTPPS were reversibly formed only at the water|DCE interface by applying appropriate potentials even when the porphyrins exist as monomers in the aqueous and organic solutions. In the HPP system, the slow aggregation process was found in the negative potential region. The spectral characteristics and the signal phase of PM-TIRF indicated that the HPP monomers were adsorbed with relatively standing orientation and that the long axis of the J-aggregates was nearly in plane of the interface. HPP was also investigated at the biomimetic phospholipid-adsorbed water|DCE interface. The competitive adsorption of neutral glycerophospholipids effectively inhibited the potential-dependent adsorption and interfacial aggregation processes of HPP. The results demonstrated that the aggregation state of the charged species can reversibly be controlled at liquid|liquid interfaces as a function of externally applied potential.

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Spectroscopic studies of molecular interaction at the liquid–liquid interface

Cited by 17 publications

References 153 publications

Total internal reflection spectroscopy for studying soft matter

Total internal reflection spectroscopy for studying soft matter

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

Potential-Induced Aggregation of Anionic Porphyrins at Liquid|Liquid Interfaces

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