In Situ PM–IRRAS Studies of Biomimetic Membranes Supported at Gold Electrode Surfaces

Kycia, Annia H.; Su, Zhixun; Brosseau, Christa L.; Lipkowski, Jacek

doi:10.1002/9781118658871.ch11

Cited by 35 publications

(81 citation statements)

References 131 publications

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“…The capacitance of these model membranes ranges from 1.7 to 4.0 μF cm −2 depending on concentration and net charge of the ganglioside introduced into the outer leaflet of the bilayer [30,39,40]. PM IRRAS studies under electrochemical control show clearly that the orientation of phosphatidylcholine molecules in both leaflets of the bilayer is affected by the addition of ganglioside molecules to the outer leaflet.…”

Section: Application Of In Situ Pm Irras For the Determination Of Thementioning

confidence: 99%

“…In this potential-dependent study of the adsorption process of cyanide ions on a silver electrode showed differences between the species adsorbed directly on the electrode surface and those dissolved in the electrolyte solution [82]. Later, structural aspects of the potential-driven adsorption-desorption process of amphiphilic organic films adsorbed on the gold electrode surface were investigated in detail [29,30,32,51].…”

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

“…PM IRRAS technique is a quantitative analytical tool which allows detailed analysis of the molecular order in various forms of supramolecular assemblies present at the investigated interface [29,30,51,83]. Due to the surface selection rule, the integral intensity of a given absorption band depends on two factors: ( ) the surface concentration ( ) of a given molecule in the film Δ ≈ 2.3 and (ii) the orientation of the transition dipole vector of a given IR absorption in this anisotropic film [29,51].…”

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

“…In this paper a brief introduction to IRRAS under electrochemical control (Section 2), limitations of IRRAS and possibilities of the extension of the application of the in situ IRRAS through modifications of the surface properties of the solid substrate, a selection of the optical window and electrolyte solution for studies of biomimetic films are discussed (Section 3). In the fourth section the application of in situ IRRAS for structural studies of potential-driven changes in lipid bilayers [9,[30][31][32][33][34][35][36] and protein films [37,38] is reviewed. Recent studies of the impact of lipid-protein interactions on the structure and stability of the membrane exposed to physiological electric fields are summarized and described [39][40][41][42].…”

Section: Introductionmentioning

confidence: 99%

“…These experimental challenges of in situ IRRAS were solved by using either a cell in Kretchmann configuration and the phenomenon of total reflection of the IR light [22] or a thin electrolyte layer cell for experiments performed under condition of the external reflection of the IR beam [16]. In the last years attenuated total reflection infrared spectroscopy (ATR IRS) [23][24][25][26][27][28] and IRRAS tech-niques [9,11,29,30] have developed into powerful methods to study in situ the structure and its changes in biomolecules present in various supramolecular assemblies on the electrode surfaces. Obviously studies of the structure and activity of biomolecules require a strict fulfilment of experimental conditions such as the composition, ionic strength and pH of the aqueous electrolyte solution, temperature or chemical nature of the used solid substrate.…”

Section: Introductionmentioning

confidence: 99%

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Application of Polarization Modulation Infrared Reflection Absorption Spectrosocpy Under Electrochemical Control for Structural Studies of Biomimetic Assemblies

Brand

2015

Zeitschrift Für Physikalische Chemie

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An ideal bioanalytical method would allow carrying out sensitive, selective, reproducible, fast, and in situ chemical measurements of the composition, structure and function of complex biological systems. Physical chemistry possesses advanced structure analyzing techniques which are suitable to solve, at a sub-molecular level, the structure of biomolecules. However, the prerequisite of the presence of the electrolyte solution limits the number of applicable structure analyzing techniques. Infrared spectroscopy is one of the most powerful analytical techniques used to identify the structure of biomolecules, monitor structural changes under various experimental environments and physical states. In addition, infrared reflection absorption spectroscopy (IRRAS) has been successfully applied to study supramolecular films at the solid|liquid interface. Assemblies of biomolecules belong to a particularly demanding because they bring specific for the maintenance of their functions experimental requirements which have to be taken into account planning in situ spectroelectrochemical experiments. In this paper potnential of in situ IRRAS under electrochemical control for studies of structural changes in assemblies of biomolecules such as lipid bilayers and protein films is described. Studies of different classes of biomolecules bring certain experimetnal conditions concerning the electrolyte composition, pH value, temperature or chemical nature of the solid support, which have to be fulfilled. Obviously, these conditons may significantly restrict the applicability of the in situ PM IRRAS. The selection of the solid substrate with required optical and electrical properties, the optical window and the electrolyte composition have to be adapted to the needs of biomolecules. Adjustement of experimetnal conditions as well as possibilites of the enlargement of the in situ PM IRRAS for studies of biomimetic assemblies is reviewed in this paper. Furthermore, experimetnal resutls reporting potenial driven changes in models of cell membranes and protein films are reviewed. Pioneering studies aiminig at the determination of structural changes in lipid membranes exposed to physiological electric fields and interacting simultaneously with protiens are described.

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Section: Application Of In Situ Pm Irras For the Determination Of Thementioning

confidence: 99%

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Application of Polarization Modulation Infrared Reflection Absorption Spectrosocpy Under Electrochemical Control for Structural Studies of Biomimetic Assemblies

Brand

2015

Zeitschrift Für Physikalische Chemie

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CD Stretching Modes are Sensitive to the Microenvironment in Ionic Liquids

Sieling

Petersen

Alpers

et al. 2021

Chemistry A European J

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Knowledge of the structure of the electrical double layer in ionic liquids (IL) is crucial for their applications in electrochemical technologies. We report the synthesis and applicability of an imidazolium-based amphiphilic ionic liquid with a perdeuterated alkyl chain for studies of electric potential-dependent rearrangements, and changes in the microenvironment in a monolayer on a Au(111) surface. Electrochemical measurements show two states of the organization of ions on the electrode surface. In situ IR spectroscopy shows that the alkyl chains in imidazolium cations change their orientation depending on the adsorption state. The methylene-d 2 stretching modes in the perdeuterated IL display a reversible, potential-dependent appearance of a new band. The presence of this mode also depends on the anion in the IL. Supported by quantum chemical calculations, this new mode is assigned to a second ν as (CD 2 ) band in alkyl-chain fragments embedded in a polar environment of the anions/solvent present in the vicinity of the imidazolium cation and electrode. It is a measure of the potential-dependent segregation between polar and nonpolar environments in the layers of an IL closest to the electrode.

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Functional activity of peptide ion channels in tethered bilayer lipid membranes: Review

Guidelli

Becucci²

2021

Electrochemical Science Adv

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Ion transport across biomembranes plays a major role in living cells. This fundamental function is normally carried out by molecules with both a hydrophobic and a hydrophilic side (amphiphilic molecules), which aggregate within the membrane forming a hydrophilic pore (the ion channel) permitting the selective translocation of permeant ions. Countless papers report the conformation of these ion channels in lipid vesicles using several techniques, such as circular dichroism and solid‐state NMR spectroscopies. However, the functional activity of ion channels can only be investigated by varying the transmembrane potential. This is also the situation in which ion channels operate in commercialized drugs with intracellular targeting activities, of great interest in pharmaceutical research. A suitable biomimetic membrane must consist of a conducting or semiconducting support, whose “heart” is a lipid bilayer in contact with the aqueous solution of interest on one side. The other side must comprise a hydrophilic region thick enough to completely decouple the lipid bilayer from the support, giving rise to a “tethered bilayer lipid membrane” (tBLM). This review aims to describe the numerous efforts made over time to approach this goal, the most recent achievements, and the perspectives of future development. Special emphasis will be placed on the electrochemical aspects of tBLMs, and a qualitative overview of the main optical and scanning probe techniques employed will be provided.

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In Situ PM–IRRAS Studies of Biomimetic Membranes Supported at Gold Electrode Surfaces

Cited by 35 publications

References 131 publications

Application of Polarization Modulation Infrared Reflection Absorption Spectrosocpy Under Electrochemical Control for Structural Studies of Biomimetic Assemblies

Application of Polarization Modulation Infrared Reflection Absorption Spectrosocpy Under Electrochemical Control for Structural Studies of Biomimetic Assemblies

CD Stretching Modes are Sensitive to the Microenvironment in Ionic Liquids

Functional activity of peptide ion channels in tethered bilayer lipid membranes: Review

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