The distance dependence of intramolecular electron-transfer rates:  importance of the nuclear factor

Isied, Stephen S.; Vassilian, Asbed; Wishart, James F.; Creutz, Carol; Schwarz, Harold A.; Sutin, Norman

doi:10.1021/ja00210a074

Cited by 148 publications

(98 citation statements)

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“…The maximum distance the electron can tunnel is a few angstroms, and the rate of electron transfer k follows the relationship [27,28] k = k 0 exp[ÀbR], where b is the decay constant, on the order of 1 Å À1 and R is the distance between donor and acceptor sites or between electrode and electroactive species. In this cited study, the value of electron rate constant falls from ca.…”

Section: Blocking Effectmentioning

confidence: 99%

Disassembly of redox responsive poly(ferrocenylsilane) multilayers: The effect of blocking layers, supporting electrolyte and polyion molar mass

Song¹,

Jańczewski²,

et al. 2013

Journal of Colloid and Interface Science

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Section: Blocking Effectmentioning

confidence: 99%

Disassembly of redox responsive poly(ferrocenylsilane) multilayers: The effect of blocking layers, supporting electrolyte and polyion molar mass

Song¹,

Jańczewski²,

et al. 2013

Journal of Colloid and Interface Science

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“…This pathway is characterized by a low value of the descriptor of the exponential distance dependence of the electron transfer rate, β ΤΒ = 2.5 ± 0.1 nm -1 , suggesting that helical segments in proteins can function as efficient channels of long-distance electron transfer. Long-range electron transfer (LRET) between various oligoproline-bridged redox pairs has been studied over the past 10 years in several laboratories (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18) with the aim of elucidating the parameters of LRET across a single peptide pathway. The choice of oligoprolines for such a study was dictated by the known ability of short H-(Pro)n-OH peptides to attain, in aqueous solution, a stable helical conformation similar to that of the 3X left-handed helix of alltrans poly-L-proline II (19)(20)(21)(22).…”

Section: Risø National Laboratory Dk-4000 Roskilde Denmarkmentioning

confidence: 99%

Long-Range Electron Transfer Between Proline-Bridged Aromatic Amino Acids

Bobrowski

Poznański

Holcman

et al. 1998

Advances in Chemistry

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Interpretation of the kinetic pulse radiolysis data for intramolecular Trp --> Tyr radical transformation in aqueous solutions of linear H-Trp-(Pro)n-Tyr-OH, n = 0-5, is presented in terms of the Marcus electron transfer theory, taking into account conformational dynamics of the molecules. For this purpose, for each peptide, representative sets of low-energy conformers were selected with the help of experimental methods ( 1 H and 13 C NMR, and circular dichroism) and modeling meth ods (molecular mechanics and dynamics ); and relative electron transfer rates averaged over all the conformers were calculated for two assumed competitive electron transfer pathways: through space (TS) and through the peptide backbone (TB). The TS rates were obtained by taking into account the overlap integrals of aromatic ring orbitals calu lated quantum mechanically. By fitting the calculated rates to the experi mental data for the rate constants for electron transfer, ket, with an exponential function appropriate for the two-pathway model, we have demonstrated that in linear short-bridged peptides (n = 0-2), electron transfer predominantly takes the TS pathway, which consists of van der Waals contacts between the aromatic rings, whereas in longer peptides (n = 3-5), it occurs exclusively by the TB pathway, which is made of a -(Pro)n-bridge in a helical conformation similar to that of all-trans poly-L-proline II. This pathway is characterized by a low value of the descriptor of the exponential distance dependence of the electron transfer rate, β ΤΒ = 2.5 ± 0.1 nm -1 , suggesting that helical segments in proteins can function as efficient channels of long-distance electron transfer.

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“…Typical for such tunnelling processes is an exponentia l decrease of the rate constant k et of electron transfer with the distance r [ 4± 6]. In general the decay of k et with distance is due to a change of the electronic factor and the nuclear factor [7]. The function may become non-exponen tial in case of strongly exergonic electron transfer [8,9].…”

Section: Introductionmentioning

confidence: 99%

Magnetic field effect as a probe of distance-dependent electron transfer in systems undergoing free diffusion

KRISSINEL¹

1999

Molecular Physics

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A theoretical analysis is presented of the problem of how distance-dependent electron transf er in photoinduced forward electron transfer followed by geminate backward electron transfer in liquid solution is re¯ected in the viscosity dependence of the magnetic ® eld e ect ( MFE) on the e ciency of free radical formation u ce in such reactions. The stochastic Liouville equation formalism is employed to model the reaction behaviour of distance-distributed, triplet-born radical pairs ( R Ps) undergoing free di usion, distance-and spin-dependent backward electron transfer, coherent and incoherent spin evolution in the ps time domain. In comparison with real systems the spin situation is simpli® ed by reducing it to a two state S , T 0 problem, yet it is parametrized in a way that allows sensible comparison of the results with those of recent experiments. It is predicted that the MFE on u ce exhibits characteristic minima in the MFE versus viscosity curves, and it is veri® ed in detail that this f eature is peculiar to the di usional model with distance-dependent electron transfer, i.e. cannot be reproduced with the simpler (`exponential') R P model employing distance-independent rate constants. Thus, the MFE versus viscosity curves are established as a genuine ® ngerprint of distance-dependent electron transfer. The theoretical results compare f avourably with recent experimental results obtained with R u III complex/methylviologen RPs.

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The distance dependence of intramolecular electron-transfer rates: importance of the nuclear factor

Cited by 148 publications

References 1 publication

Disassembly of redox responsive poly(ferrocenylsilane) multilayers: The effect of blocking layers, supporting electrolyte and polyion molar mass

Disassembly of redox responsive poly(ferrocenylsilane) multilayers: The effect of blocking layers, supporting electrolyte and polyion molar mass

Long-Range Electron Transfer Between Proline-Bridged Aromatic Amino Acids

Magnetic field effect as a probe of distance-dependent electron transfer in systems undergoing free diffusion

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