Kinetics of the ionization of monoalkylbenzenes and nitroalkanes in polar solvents. 2. Calculation of the outer-sphere reorganization energy

1989 ◽  
Vol 38 (2) ◽  
pp. 277-279
Author(s):  
�. D. German ◽  
N. G. Zharova ◽  
I. O. Shapiro
Keyword(s):  
Reorganization Energy ◽  
Outer Sphere ◽  
Polar Solvents ◽  
Kinetics Of

Kinetics of N-substituted phenothiazines and N-substituted phenoxazines oxidation catalyzed by fungal laccases

2009 ◽  
Vol 4 (1) ◽  
pp. 62-67 ◽  
Author(s):  
Lidija Tetianec ◽  
Juozas Kulys
Keyword(s):  
Electron Transfer ◽  
Redox Potential ◽  
Reorganization Energy ◽  
Outer Sphere ◽  
Initial Reaction Rate ◽  
Initial Reaction ◽  
Type I ◽  
Electron Transfer Mechanism ◽  
Recombinant Laccase ◽  
Kinetics Of

AbstractLaccase-catalyzed oxidation of N-substituted phenothiazines and N-substituted phenoxazines was investigated at pH 5.5 and 25°C. The recombinant laccase from Polyporus pinsitus (rPpL) and the laccase from Myceliophthora thermophila (rMtL) were used. The dependence of initial reaction rate on substrate concentration was analyzed by applying the laccase action scheme in which the laccase native intermediate (NI) reacts with a substrate forming reduced enzyme. The reduced laccase produces peroxide intermediate (PI) which in turn decays to the NI. The calculated constant (kox) values of the PI formation are (6.1±3.1)×105 M−1s−1 for rPpL and (2.5±0.9)×104 M−1s−1 for rMtL. The bimolecular constants of the reaction of the native intermediate with electron donor (kred) vary in the interval from 2.2×105 to 2.1×107 M−1s−1 for rPpL and from 1.3×102 to 1.8×105 M-1s−1 for rMtL. The larger reactivity of rPpL in comparison to rMtL is associated with the higher redox potential of type I Cu of rPpL. The variation of kred values for both laccases correlates with the change of the redox potential of substrates. Following outer sphere (Marcus) electron transfer mechanism the calculated activationless electron transfer rate and the apparent reorganization energy are 5.0×107 M−1s−1 and 0.29 eV, respectively.

Evidences of Conformational Fluctuations of 2-methylaminofluorenone and 2-dimethylaminofluorenone in Polar Solvents

2004 ◽  
Vol 59 (3) ◽  
pp. 105-112 ◽  
Author(s):  
M. Józefowicza ◽  
J. R. Heldta ◽  
J. Heldta ◽  
J. Heldta
Keyword(s):  
Fluorescence Spectra ◽  
Polar Solvent ◽  
Reorganization Energy ◽  
Outer Sphere ◽  
Fluorescence Decay ◽  
Absorption And Fluorescence Spectra ◽  
Exponential Functions ◽  
Polar Solvents ◽  
Ground State Dipole Moment ◽  
Reorganization Energies

The absorption and fluorescence spectra of 2-methylaminofluorenone (2MAFl) and 2-dimethylaminofluorenone (2DMAFl) were determined at 293 K in a variety of solvents with different polarities. The spectral data were used, in combination with the 2MAFl and 2DMAFl ground state dipole moment (μg), to evaluate μe of the S1 state, to determine the outer-sphere solvent reorganization energy λouter, and the intramolecular reorganization energies: λ1 (associated with vibrations for which hv < kT) and λi(hv > kT). At 77 K the fluorescence spectra in a non-polar solvent are shifted to longer wavelengths. In polar solvents, for both molecules the behavior is opposite. The fluorescence decay data for 2MAFl and 2DMAFl in non-polar solvents are very well fitted by oneexponential functions, while in polar solvents by two-exponential functions. The spectroscopic data distinctly show that both studied molecules in polar solvents form an inhomogeneous emitting system.

scholarly journals Influence of a nearby substrate on the reorganization energy of hole exchange between dye molecules

2015 ◽  
Vol 17 (11) ◽  
pp. 7345-7354 ◽  
Author(s):  
Fabian Manke ◽  
Jarvist M. Frost ◽  
Valérie Vaissier ◽  
Jenny Nelson ◽  
Piers R. F. Barnes
Keyword(s):  
Reorganization Energy ◽  
Outer Sphere ◽  
Dye Molecules ◽  
Polar Solvents ◽  
Hole Transfer ◽  
Dielectric Substrates ◽  
Reorganisation Energy

The outer-sphere reorganisation energy for hole transfer between dye molecules in polar solvents is reduced by around 20% by dielectric substrates.

scholarly journals Outer-sphere effects on ligand-field excited-state dynamics: solvent dependence of high-spin to low-spin conversion in [Fe(bpy)3]2+

2020 ◽  
Vol 11 (20) ◽  
pp. 5191-5204 ◽  
Author(s):  
Jennifer N. Miller ◽  
James K. McCusker
Keyword(s):  
Excited State ◽  
Reorganization Energy ◽  
Outer Sphere ◽  
Ligand Field ◽  
Spin Conversion ◽  
Energy Effect ◽  
Time Resolved ◽  
Excited State Dynamics ◽  
State Recovery ◽  
Solvent Dependence

Time-resolved spectroscopic measurements of ground-state recovery for [Fe(bpy)3]2+ reveal that the solvent can induce an outer-sphere reorganization energy effect on excited-state dynamics involving metal-centered ligand-field electronic states.

Electrode kinetics of Eu3+/Eu2+ reaction by cyclic voltammetry

1982 ◽  
Vol 47 (7) ◽  
pp. 1773-1779 ◽  
Author(s):  
T. P. Radhakrishnan ◽  
A. K. Sundaram
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Outer Sphere ◽  
Electrode Reaction ◽  
Transfer Reactions ◽  
Cyclic Voltammetric ◽  
Edta Solution ◽  
Kinetics Of ◽  
Activated Complex ◽  
Good Agreement

The paper is a detailed study of the cyclic voltammetric behaviour of Eu3+ at HMDE in molar solutions of KCl, KBr, KI, KSCN and in 0.1M-EDTA solution with an indigenously built equipment. The computed values of the rate constants at various scan rates show good agreement with those reported by other electrochemical methods. In addition, the results indicate participation of a bridged activated complex in the electron-transfer step, the rate constants showing the trend SCN- > I- > Br- > Cl- usually observed for bridging order of these anions in homogeneous electron-transfer reactions. The results for Eu-EDTA system, however, indicate involvement of an outer sphere activated complex in the electrode reaction.

Complexation Kinetics of Copper(II) and Nickel(II) with Macrocycles:  Identification of an Outer-Sphere Chelate Effect

2007 ◽  
Vol 46 (10) ◽  
pp. 4002-4009 ◽  
Author(s):  
Nichola McCann ◽  
Geoffrey A. Lawrance ◽  
Yorck-Michael Neuhold ◽  
Marcel Maeder
Keyword(s):  
Outer Sphere ◽  
Chelate Effect ◽  
Kinetics Of ◽  
Complexation Kinetics

1H and 13C NMR Study of Proton Transfer in Azoles. Mechanism of Proton Transfer in Pyrazole in Solutions Containing bis-(Acetylacetonato) Nickel (II)

1976 ◽  
Vol 31 (7-8) ◽  
pp. 353-360 ◽  
Author(s):  
V. N. Babin ◽  
E. B. Zavelovidi ◽  
E. I. Fedin
Keyword(s):  
Proton Transfer ◽  
Ligand Exchange ◽  
Hyperfine Coupling ◽  
Outer Sphere ◽  
Coupling Constants ◽  
1H And 13C Nmr ◽  
Nmr Study ◽  
Nmr Techniques ◽  
Kinetics Of ◽  
C Nmr

Abstract Proton Transfer, Pyrazole, Outer-Sphere Coordination Proton transfer in pyrazole systems involving interaction with a paramagnetic transition metal complex has been studied with 1H and 13C NMR techniques. Kinetics of the ligand exchange in the pyrazole complex of bis-(acetylacetonato) nickel (II) has been investigated, and hyperfine coupling constants for the interaction of the nickel unpaired electron with the ligand nuclei in the complex have been determined. Catalytic admixtures of bis-(acetylacetonato) nickel (II) are shown to modify the mechanism of the proton transfer in pyrazole. The spectral data are discussed in terms of outer-sphere coordination and cooperative proton transfer effects.

scholarly journals Kinetics of Reduction of Fe(III) Complexes by Outer Membrane Cytochromes MtrC and OmcA of Shewanella oneidensis MR-1

2008 ◽  
Vol 74 (21) ◽  
pp. 6746-6755 ◽  
Author(s):  
Zheming Wang ◽  
Chongxuan Liu ◽  
Xuelin Wang ◽  
Matthew J. Marshall ◽  
John M. Zachara ◽  
...  
Keyword(s):  
Redox Potential ◽  
Outer Membrane ◽  
Kinetic Data ◽  
Shewanella Oneidensis ◽  
Reorganization Energy ◽  
Second Order ◽  
Metal Species ◽  
Stopped Flow ◽  
Kinetics Of ◽  
Kinetics Of Reduction

ABSTRACT Because of their cell surface locations, the outer membrane c-type cytochromes MtrC and OmcA of Shewanella oneidensis MR-1 have been suggested to be the terminal reductases for a range of redox-reactive metals that form poorly soluble solids or that do not readily cross the outer membrane. In this work, we determined the kinetics of reduction of a series of Fe(III) complexes with citrate, nitrilotriacetic acid (NTA), and EDTA by MtrC and OmcA using a stopped-flow technique in combination with theoretical computation methods. Stopped-flow kinetic data showed that the reaction proceeded in two stages, a fast stage that was completed in less than 1 s, followed by a second, relatively slower stage. For a given complex, electron transfer by MtrC was faster than that by OmcA. For a given cytochrome, the reaction was completed in the order Fe-EDTA > Fe-NTA > Fe-citrate. The kinetic data could be modeled by two parallel second-order bimolecular redox reactions with second-order rate constants ranging from 0.872 μM−1 s−1 for the reaction between MtrC and the Fe-EDTA complex to 0.012 μM−1 s−1 for the reaction between OmcA and Fe-citrate. The biphasic reaction kinetics was attributed to redox potential differences among the heme groups or redox site heterogeneity within the cytochromes. The results of redox potential and reorganization energy calculations showed that the reaction rate was influenced mostly by the relatively large reorganization energy. The results demonstrate that ligand complexation plays an important role in microbial dissimilatory reduction and mineral transformation of iron, as well as other redox-sensitive metal species in nature.

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