Charge transfer and transport in DNA.

We explore charge migration in DNA, advancing two distinct mechanisms of charge separation in a donor (d)-bridge ([Bj])-acceptor (a) system, where [Bj] = B1,B2, . , BN are the N-specific adjacent bases of B-DNA: (i) two-center unistep superexchange induced charge transfer, d*[Bj]a --> d[Bj]a+/-, and (ii) multistep charge transport involves charge injection from d* (or d+) to [Bj], charge hopping within [Bj], and charge trapping by a. For off-resonance coupling, mechanism i prevails with the charge separation rate and yield exhibiting an exponential dependence approximately exp(-betaR) on the d-a distance (R). Resonance coupling results in mechanism ii with the charge separation lifetime tau approximately Neta and yield Y approximately (1 + Neta)-1 exhibiting a weak (algebraic) N and distance dependence. The power parameter eta is determined by charge hopping random walk. Energetic control of the charge migration mechanism is exerted by the energetics of the ion pair state dB1+/-B2 . BNa relative to the electronically excited donor doorway state d*B1B2 . BNa. The realization of charge separation via superexchange or hopping is determined by the base sequence within the bridge. Our energetic-dynamic relations, in conjunction with the energetic data for d*/d- and for B/B+, determine the realization of the two distinct mechanisms in different hole donor systems, establishing the conditions for "chemistry at a distance" after charge transport in DNA. The energetic control of the charge migration mechanisms attained by the sequence specificity of the bridge is universal for large molecular-scale systems, for proteins, and for DNA.

[1]  J. Barton,et al.  Oxidative charge transfer To repair thymine dimers and damage guanine bases in DNA assemblies containing tethered metallointercalators. , 1998, Biochemistry.

[2]  E. Meggers,et al.  Electron Transfer through DNA in the Course of Radical-Induced Strand Cleavage. , 1998, Angewandte Chemie.

[3]  Joseph Klafter,et al.  Geometric versus Energetic Competition in Light Harvesting by Dendrimers , 1998 .

[4]  S. Mukamel,et al.  Solvent Reorganization in Long-Range Electron Transfer: Density Matrix Approach , 1998 .

[5]  K. Fukui,et al.  Distance Dependence of Photoinduced Electron Transfer in DNA , 1998 .

[6]  Kendall N. Houk,et al.  EFFECT OF GUANINE STACKING ON THE OXIDATION OF 8-OXOGUANINE IN B-DNA , 1998 .

[7]  G. Schuster,et al.  Intramolecular Photoinduced Electron Transfer to Anthraquinones Linked to Duplex DNA: The Effect of Gaps and Traps on Long-Range Radical Cation Migration , 1997 .

[8]  Joshua Jortner,et al.  Electron transfer via bridges , 1997 .

[9]  S. Greenfield,et al.  Distance-dependent electron transfer in DNA hairpins. , 1997, Science.

[10]  J. Barton,et al.  Long-range oxidation of guanine by Ru(III) in duplex DNA. , 1997, Chemistry & biology.

[11]  J. Barton,et al.  OXIDATION OF GUANINE IN DNA BY RU(PHEN)2(DPPZ)3+ USING THE FLASH-QUENCH TECHNIQUE , 1997 .

[12]  J. Barton,et al.  Oxidative Thymine Dimer Repair in the DNA Helix , 1997, Science.

[13]  D. Beratan,et al.  DNA Is Not a Molecular Wire: Protein-like Electron-Transfer Predicted for an Extended π-Electron System , 1996 .

[14]  Jacqueline K. Barton,et al.  Oxidative DNA damage through long-range electron transfer , 1996, Nature.

[15]  M R Arkin,et al.  Rates of DNA-Mediated Electron Transfer Between Metallointercalators , 1996, Science.

[16]  J. Barton,et al.  Os(phen)2dppz2+ in Photoinduced DNA-Mediated Electron Transfer Reactions , 1996 .

[17]  Markus Sauer,et al.  NUCLEOBASE-SPECIFIC QUENCHING OF FLUORESCENT DYES. 1. NUCLEOBASE ONE-ELECTRON REDOX POTENTIALS AND THEIR CORRELATION WITH STATIC AND DYNAMIC QUENCHING EFFICIENCIES , 1996 .

[18]  D. Breslin,et al.  Anthraquinone Photonucleases: Mechanisms for GG-Selective and Nonselective Cleavage of Double-Stranded DNA , 1996 .

[19]  N. Turro,et al.  Excited state properties of Rh(phi)2(phen)3+ and related complexes: a strong photooxidant , 1996 .

[20]  John M. Warman,et al.  DNA: a molecular wire? , 1996 .

[21]  M. Michel-beyerle,et al.  A kinetic analysis of the primary charge separation in bacterial photosynthesis. Energy gaps and static heterogeneity , 1995 .

[22]  J. Deisenhofer,et al.  Crystal structure of DNA photolyase from Escherichia coli. , 1995, Science.

[23]  J. Barton,et al.  ELECTRON TRANSFER BETWEEN METALLOINTERCALATORS BOUND TO DNA : SPECTRAL IDENTIFICATION OF THE TRANSIENT INTERMEDIATE , 1995 .

[24]  M R Arkin,et al.  Fast photoinduced electron transfer through DNA intercalation. , 1994, Proceedings of the National Academy of Sciences of the United States of America.

[25]  A. Sancar.  Structure and function of DNA photolyase. , 1994, Biochemistry.

[26]  M R Arkin,et al.  Long-range photoinduced electron transfer through a DNA helix. , 1993, Science.

[27]  A. Harriman,et al.  Dynamics of electron transfer between intercalated polycyclic molecules: effect of interspersed bases , 1992 .

[28]  D. D. Eley.  Studies of Organic Semiconductors for 40 Years—I The Mobile π-Electron—40 Years on , 1989 .

[29]  Protein structure : molecular and electronic reactivity , 1987 .

[30]  R. Marcus,et al.  Electron transfers in chemistry and biology , 1985 .

[31]  M. Newton,et al.  Electron Transfer Reactions in Condensed Phases , 1985 .

[32]  D. Sherrington.  Stochastic Processes in Physics and Chemistry , 1983 .

[33]  Charles E. Swenberg,et al.  Electronic Processes in Organic Crystals , 1982 .

[34]  A. Weller.  Photoinduced Electron Transfer in Solution: Exciplex and Radical Ion Pair Formation Free Enthalpies and their Solvent Dependence , 1982 .

[35]  N. Kampen,et al.  Stochastic processes in physics and chemistry , 1981 .

[36]  Bruce J. West,et al.  Analytic theory of extrema. III. Results for master equations with application to unimolecular decomposition , 1980 .

[37]  J. Ross,et al.  On the theory of unimolecular reactions: Application of mean first passage time to reaction rates , 1978 .

[38]  Joshua Jortner,et al.  Temperature dependent activation energy for electron transfer between biological molecules , 1976 .

[39]  S. Efrima,et al.  Vibrational effects in outer-sphere electron-transfer reactions in polar media , 1976 .

[40]  J. Ulstrup,et al.  The effect of intramolecular quantum modes on free energy relationships for electron transfer reactions , 1975 .

[41]  J. Logan,et al.  Thermal electron transfer reactions in polar solvents , 1974 .

[42]  M. Baur,et al.  Charge and excitation migration in DNA chains , 1974 .

[43]  S. Suhai.  Charge Carrier Mobilities in Periodic DNA Models , 1972 .

[44]  D. Rehm,et al.  Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer , 1970 .

[45]  J. Jortner,et al.  Triplet-exciton dynamics in polyadenilic acid. , 1968, The Journal of chemical physics.

[46]  A. Szöke,et al.  Diffusion of Triplet Excitons in Crystalline Anthracene , 1966 .

[47]  W. Fredericks,et al.  On the Diffusion Parameters of Plumbous Ions in KCl , 1965 .

[48]  J. Ladik,et al.  Energy-Band Calculations for Periodic DNA Models in the Hückel Approximation , 1965 .

[49]  S. Rice,et al.  Erratum: Exchange Effects on the Electron and Hole Mobility in Crystalline Anthracene and Naphthalene , 1965 .

[50]  Rudolph A. Marcus,et al.  Chemical and Electrochemical Electron-Transfer Theory , 1964 .

[51]  S. Rice,et al.  On the Excess Electron and Hole Band Structures and Carrier Mobility in Naphthalene, Anthracene, and Several Polyphenyls , 1963 .

[52]  D. D. Eley,et al.  Semiconductivity of organic substances. Part 9.—Nucleic acid in the dry state , 1962 .

[53]  H. Mcconnell,et al.  Intramolecular Charge Transfer in Aromatic Free Radicals , 1961 .

[54]  R. Dietzel,et al.  Die neuere Entwicklung der Lebensmittelchemie. (2. Bericht) , 1924 .