Vlad Zamlynny

Electrochemical and photon polarization modulation infrared reflection absorption spectroscopy study of the electric field driven transformations of a phospholipid bilayer supported at a gold electrode surface.

Electrochemistry and polarization modulation Fourier transform infrared reflection absorption spectroscopy (PM-FTIRRAS) was employed to investigate fusion of small unilamellar vesicles of 1,2dioyl-sn-glycero-3-phosphatidyl choline (DOPC) onto the Au(111) electrode. Electrochemical studies demonstrated that the DOPC vesicles fuse and spread onto the gold electrode surface at small charge densities -8 microC cm(-2)<sigmaM<0 microC cm(-2)(if the static electric field is <2 x 10(8) V/m) to form a bilayer. At sigmaM<-8 microC cm(-2), the film is detached from the electrode surface; however, the film remains in close proximity to the surface. The PM-FTIRRAS experiments demonstrated that the field-driven transformation of the film involves changes in hydration, orientation, and conformation in the polar headgroup region and that changes in the packing and tilt of the acyl chains are consequences of the headgroup rearrangements.

Electrochemical and PM-IRRAS studies of potential controlled transformations of phospholipid layers on Au(111) electrodes

Chronocoulometry and photon polarisation modulation infrared reflection absorption spectroscopy (PM-IRRAS) have been employed to study the fusion of dimyristoylphosphatidylcholine (DMPC) vesicles onto a Au(111) electrode surface. The results show that fusion of the vesicles is controlled by the electrode potential or charge at the electrode surface (sigmaM). At charge densities of -15 microC cm(-2) < sigmaM < 0 microC cm(-2), DMPC vesicles fuse to form a condensed film. When sigmaM < -15 microC cm(-2), de-wetting of the film from the electrode surface occurs. The film is detached from the electrode surface; however, phospholipid molecules remain in its close proximity in an ad-vesicle state. The state of the film can be conveniently changed by adjustment of the potential applied to the gold electrode. PM-IRRAS experiments demonstrated that the potential-controlled transitions between various DMPC states proceed without conformational changes and changes in the packing of the acyl chains of DMPC molecules. However, a remarkable change in the tilt angle of the acyl chains with respect to the surface normal occurs when ad-vesicles spread to form a film at the gold surface. When the bilayer is formed at the gold surface, the acyl chains of DMPC molecules are significantly tilted. The IR spectra have also demonstrated a pronounced change in the hydration of the polar head region that accompanies the spreading of ad-vesicles into the film. For the film deposited at the electrode surface, the infrared results showed that the temperature-controlled phase transition from the gel state to the liquid crystalline state occurs within the same temperature range as that observed for aqueous solutions of vesicles. The results presented in this work show that PM-FTIR spectroscopy, in combination with electrochemical techniques, is an extremely powerful tool for the study of the structure of model membrane systems at electrode surfaces.

In situ IR reflectance absorption spectroscopy studies of pyridine adsorption at the Au(110) electrode surface

In situ subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) has been employed to study the adsorption of pyridine at the Au(110) electrode surface. The IR spectra provide direct spectroscopic evidence that pyridine molecules adsorb, bonded through the nitrogen atom to the Au(110) surface, in the whole range of electrode potentials. IR spectroscopy was further used to study the effect of the electrode potential on the tilt angle (angle between the C2 axis of the molecule and the direction normal to the surface) of the adsorbed molecules. The IR data consistently show that the tilt angle decreases progressively with increasing electrode potential (charge on the metal). The change of the tilt angle may be described in terms of the electric field–dipole interaction and is caused by the dielectric saturation phenomenon. At low charge density, where the field is small, the film of N-bonded pyridine molecules is less rigid and the molecules exhibit a waving motion. This motion is restrained significantly in the presence of a large electrostatic field (high charge density at the metal). The monolayer of adsorbed molecules can be considered as being effectively frozen at sufficiently high charge densities.

In situ infrared Reflection Absorption Spectroscopy studies of the interaction of Nafion® with the Pt electrode surface

Abstract Infrared Reflection Absorption Spectroscopy (IRRAS) has been applied to study the nature of the co-ordination of Nafion® to a Pt electrode surface. The experiments have been carried out using a Pt electrode coated with a thin film of Nafion® assembled into a thin layer spectroelectrochemical cell. The potential modulation or the subtractively normalized interfacial Fourier transform infrared reflection spectroscopy (SNIFTIRS) experiments have been performed, in order to distinguish between the bulk properties of the Nafion® membrane and the properties of the membrane at the interace with the Pt electrode. The results showed that the interaction between the membrane and a Pt electrode resembles the interaction between a Pt electrode and a sulfuric acid solution.

Methylene Blue Incorporation into Alkanethiol SAMs on Au(111): Effect of Hydrocarbon Chain Ordering

A detailed polarization modulation infrared reflection absorption spectroscopy, scanning tunneling microscopy, and electrochemical study on methylene blue (MB) incorporation into alkanethiolate self-assembled monolayers (SAMs) on Au(111) is reported. Results show that the amount of MB incorporated in the SAMs reaches a maximum for intermediate hydrocarbon chain lengths (C10-C12). Well-ordered SAMs of long alkanethiols (C > C12) hinder the incorporation of the MB molecules into the SAM. On the other hand, less ordered SAMs of short alkanethiols (C < or = C6) are not efficient to retain the MB incorporated through the defects. For C12 the amount of incorporated MB increases as the SAM disorder is increased. This information is essential to the design of efficient thiol-based Au vectors for transport and delivery of molecules as well as thiol-based Au devices for molecular sensing.

Neutron reflectivity studies of field driven transformations in a monolayer of 4-pentadecyl pyridine at Au electrode surfaces

Neutron reflectometry (NR) has been employed to study the structure and composition of thin films formed by 4-pentadecylpyridine (C15-4Py) at a gold electrode surface. The thickness and the water content of films of C15-4Py have been measured as a function of the potential applied to the electrode. At positive potentials, where condensed film is formed, the monolayer contains defects that are filled with water. At very negative potentials, the film is desorbed from the electrode surface. NR has demonstrated that, at these potentials, the amphiphilic molecules remain in close proximity to the gold surface as a thicker and water rich film. # 2003 Elsevier B.V. All rights reserved.