Chemistry Commons^™

Voltammetry And Spectroelectrochemistry Of Tcnq In Acetonitrile/Rtil Mixtures, Abderrahman Atifi, Michael D. Ryan

Chemistry Faculty Research and Publications

Understanding the solvation and ion-pairing interactions of anionic substrates in room-temperature ionic liquids (RTIL) is key for the electrochemical applications of these new classes of solvents. In this work, cyclic voltammetry and visible and infrared spectroelectrochemistry of tetracyanoquinodimethane (TCNQ) was examined in molecular (acetonitrile) and RTIL solvents, as well as mixtures of these solvents. The overall results were consistent with the formation of RTIL/acetonitrile nanodomains. The voltammetry indicated that the first electrogenerated product, TCNQ⁻, was not incorporated into the RTIL nanodomain, while the second electrogenerated product, TCNQ²⁻, was strongly attracted to the RTIL nanodomain. The visible …

Altering The Coordination Of Iron Porphyrins By Ionic Liquid Nanodomains In Mixed Solvent Systems, Abderrahman Atifi, Michael D. Ryan

Chemistry Faculty Research and Publications

The solvent environment around iron porphyrin complexes was examined using mixed molecular/RTIL (room temperature ionic liquid) solutions. The formation of nanodomains in these solutions provides different solvation environments for substrates that could have significant impact on their chemical reactivity. Iron porphyrins (Fe(P)), whose properties are sensitive to solvent and ligation changes, were used to probe the molecular/RTIL environment. The addition of RTILs to molecular solvents shifted the redox potentials to more positive values. When there was no ligation change upon reduction, the shift in the E° values were correlated to the Gutmann acceptor number, as was observed for other …

Spectroelectrochemistry And Voltammetry Of Metalloporphinones, Florentina Tutunea

Dissertations (1934 -)

Metalloporphinones have been found in a number of enzymes involved in nitrogen metabolism. The emphasis of this research project has been to develop spectroscopic markers in order to identify metal versus porphinone reduction. The carbonyl group in the porphinone has a very strong signal which is quite sensitive to the extent of reduction of the porphinone macrocycle.

The spectral change makes IR an important tool in the process of structure determination of metalloporphyrins because the carbonyl group shift can be correlated with the metal oxidation state. It was observed from previously published studies that a higher metal oxidation state moves …

Use Of Factor Analysis In Multi‐Electron Spectroelectrochemistry, Michael D. Ryan, Robert L. Keesey

Chemistry Faculty Research and Publications

Spectroelectrochemistry and voltammetry contain both unique and complementary information. For multielectron transfers, information on each electron exchange is only directly accessible in the voltammetric data if the potentials are well separated so that two distinct waves can be observed. If the E°’s are close together, the voltammetric data will contain the sum of the two exchanges which can only be deconvoluted by modeling the system and solving the appropriate equations. On the other hand, the spectroscopic data contains direct information on each electron exchange even when the E°’s are close together. Unfortunately, this information cannot be readily extracted if the …

Direct Voltammetric Observation Of Redox Driven Changes In Axial Coordination And Intramolecular Rearrangement Of The Phenylalanine-82-Histidine Variant Of Yeast Iso-1-Cytochrome C, Benjamin A. Feinberg, Xiangjun Liu, Michael D. Ryan, Abel Schejter, Chongyao Zhang, Emanuel Margoliash

Chemistry Faculty Research and Publications

Direct square-wave and cyclic voltammetric electrochemical examination of the yeast iso-1-cytochrome c Phe82His/Cys102Ser variant revealed the intricacies of redox driven changes in axial coordination, concomitant with intramolecular rearrangement. Electrochemical methods are ideally suited for such a redox study, since they provide a direct and quantitative visualization of specific dynamic events. For the iso-1-cytochrome c Phe82His/Cys102Ser variant, square-wave voltammetry showed that the primary species in the reduced state is the Met₈₀-Fe²⁺-His₁₈ coordination form, while in the oxidized state the His₈₂-Fe³⁺-His₁₈ form predominates. The addition or removal of an electron to the …