OTTLE optically transparent thin layer

The question of whether electrons added to a complex ion become localized or delocalized is important, not only for the type of complex mentioned above, but also for much wider ranges of complexes. For such studies the use of an OTTLE (optically transparent thin layer electrochemical) cell is most appropriate... 

OTTLE optically transparent thin-layer electrode... 

OTTLE optically transparent thin layer electro- PASS polymer analysis and simulation soft-... 

We have been able to develop OTTLE (Optically Transparent Thin-Layer Electrochemical) cells with pathlengths as low as a few... 

Method Abs, chemical reduction, monitored by absorption spectroscopy CD, chemical reduction, monitored by CD spectroscopy CD/OTTLE, electrochemical reduction using an optically transparent thin layer (OTTLE) cell, monitored by CD spectroscopy CV, cyclic voltammetry EPR, chemical reduction, monitored by EPR. 

An optically transparent thin-layer electrode (OTTLE) study18 revealed that the visible spectra of the reduced forms of [Ru(bipy)3]2+ derivatives can be separated into two classes. Type A complexes, such as [Ru(bipy)3]2+, [Ru(L7)3]2+, and [Ru(L )3]2+ show spectra on reduction which contain low-intensity (e< 2,500 dm3 mol-1 cm-1) bands these spectra are similar to those of the reduced free ligand and are clearly associated with ligand radical anions. In contrast, type B complexes such as [Ru(L8)3]2+ and [Ru(L9)3]2+ on reduction exhibit spectra containing broad bands of greater intensity (1,000 [Pg.584]

The other popular approach to in situ spectroelectrochemistry is based on the use of an OTE electrode in a thin-layer, optically transparent thin layer electrode (OTTLE), cell. A schematic representation of one design of OTTLE cell is shown in Figure 2.105. 

Figure 2.105 Optically transparent thin layer electrochemical (OTTLE) cell. A = PTFE cell body, B = 13 x 2 mm window, (C and E) = PTFE spacers, D = gold minigrid electrode, F = 25 mm window, G = pressure plate, H = gold working electrode contact, 1 = reference electrode compartment, J = silver wire, K = auxiliary electrode and L = solution presaturator. From Ranjith...

In situ photoacoustic spectroscopy has been used to study the redox process on the surface of an electrode using copper metal in alkaline solution.1029 The E° values of copper(II) Schiff base complexes1030 absorbed on optically transparent thin-layer electrodes (OTTLE) have been... 

Figure 3.16A shows spectra of o-tolidine in an optically transparent thin-layer electrode (OTTLE) for a series of applied potentials. Curve a was recorded after application of +0.800 V, which caused complete oxidation of o-tolidine ([0]/[R] > 1000). Curve g was recorded after application of +0.400 V, causing complete reduction ([0]/[R] < 0.001). The intermediate spectra correspond to intermediate values of Eapplied. Since the absorbance at 438 nm reflects the amount of o-tolidine in the oxidized form via Beer s law, the ratio [0]/[RJ that corresponds to each value of Eapplied can be calculated from the spectra by Equation 3.18. 

A vacuum spectroelectrochemical cell that also contains an optically transparent thin-layer electrode (OTTLE) is shown in Figures 18.16 and 18.17. The cell can function either as a spectroelectrochemical cell employing an OTTLE or as an electrochemical cell for voltammetric measurements. This low-volume cell is useful for UV/Vis spectral studies in nonaqueous solvents when the reduction product is sensitive to traces of molecular oxygen present in the solvent. The cell is physically small enough to fit inside the sample compartment of the spectrophotometer. The performance of such a cell was evaluated from visible spectroscopy and coulometry of methyl viologen in propylene carbonate [45]. 

Figure 18.16 Vacuum electrochemical cells (A) vacuum spectroelectrochemical cell that contains an optically transparent thin-layer electrode (OTTLE) and (B) electrochemical cell assembly. [From Ref. 45, with permission.]...

Methods. All solutions were prepared to be ImM Cytochrome c, 0.1mM DCIP, 0.10M alkali halide, and 0.10M phosphate buffer at pH 7.0 or pD 7.0. The DCIP served as a mediator-titrant for coupling the Cytochrome c with the electrode potential. E° values were measured using a previously described spectropotentiostatic technique using an optically transparent thin-layer electrode (OTTLE) (7,11,12). This method involved incrementally converting the cytochrome from its fully oxidized to fully reduced state by a series of applied potentials. For each potential a spectrum was recorded after equilibrium was attained. The formal redox potential was obtained from a Nernst plot. The n value... 

Optically transparent electrode — (OTE), the electrode that is transparent to UV-visible light. Such an electrode is very useful to couple electrochemical and spectroscopic characterization of systems (- spectroelectro-chemistry). Usually the electrodes feature thin films of metals (Au, Pt) or semiconductors (In203, SnCb) deposited on transparent substrate (glass, quartz, plastic). Alternatively, they are in a form of fine wire mesh minigrids. OTE are usually used to obtain dependencies of spectra (or absorbance at given wavelengths) on applied potentials. When the -> diffusion layer is limited to a thin layer (i.e., by placing another, properly spaced, transparent substrate parallel to the OTE), bulk electrolysis can be completed in a few seconds and, for -> reversible or - quasireversible systems, equilibrium is reached for the whole solution with the electrode potential. Such OTEs are called optically transparent thin-layer electrodes or OTTLE s. 

Figure 28. Configurations for spectroelectrochemistry. A) optically transparent electrode B) optically transparent thin-layer electrode (OTTLE) C) Internal reflection spectroscopy, and D) specular reflectance spectroscopy.

Other spectroscopic techniques that have been used with electrochemistry to probe nanoparticles include electronic and vibrational spectroscopies. The spec-troelectrochemistry of nanosized silver particles based on their interaction with planar electrodes has been studied recently [146] using optically transparent thin layer electrodes (OTTLE). Colloidal silver shows a surface plasmon resonance absorption at 400 nm corresponding to 0.15 V vs. Ag/AgCl. This value blue shifts to 392 nm when an Au mesh electrode in the presence of Ag colloid is polarized to —0.6 V (figure 20.12). The absorption spectrum is reported to be quite reproducible and reversible. This indicates that the electron transfer occurs between the colloidal particles and a macroelectrode and vice versa. The kinetics of electron transfer is followed by monitoring the absorbance as a function of time. The use of an OTTLE cell ensures that the absorbance is due to all the particles in the cell between the cell walls and the electrode. The distance over which the silver particles will diffuse has been calculated to be 80 pm in 150 s, using a diffusion coef-... 

The optically transparent thin-layer electrochemical (or OTTLE) cell has caught on to the greatest extent for UV-vis spectroelectrochemistry (Figure l).1-3 The OTTLE also offers a way to measure both the redox potential and the n-value without requiring knowledge of the electron... 

Figure 3 Spectroelectrochemical cell configurations (1) transmission cell with optically transparent electrode (OTE) (2) transmission optically transparent thin layer electrode cell (OTTLE) with OTE (3) sandwich OTTLE cell with minigrid or reticulated carbon (RVC) electrode (4) long optical path-length cell (LOPTC) with light parallel to electrode surface (5) double transmission reflection cell (6) internal...

Optically Transparent Thin-Layer Cell (OTTLE)... 

Fe -"Fe -") species (NC)4Fe(p-bmtz)Fe(CN)4r 6 ( c= 10 in CH3CN/O.I M Bu4NPF6) from an experiment with an optically transparent thin-layer electrolysis (OTTLE) cell with Pt gauze working electrode is only one form of graphical representation, difference spectra or three-dimensional plots are also being used. ... 

OTTLE cell Optically transparent thin-layer electrochemical cell... 

The particular advantage of this optically transparent thin-layer electrode (OTTLE) is that bulk electrolysis is achieved in a few seconds, so that (for a chemically reversible system) the whole solution reaches an equilibrium with the electrode potential, and spectral data can be gathered on a static solution composition. 

The technique of optically transparent thin-layer electrochemistry (ottle) was first applied to the characterization of the stoichiometry and thermodynamics of horse heart cytochrome c by Heineman et alP This report showed how the special features of ottle can be combined with optical monitoring of a mediated biological electrode response to provide a simple, accurate, and precise means of characterizing the stoichiometry and thermodynamics of a biological molecule. The mechanism of mediation is described by the following equations ... 

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