Hole size and energetics in double helical DNA: Competition between quantum delocalization and solvation localization

被引:92
作者
Kurnikov, IV
Tong, GSM
Madrid, M
Beratan, DN
机构
[1] Duke Univ, Dept Chem, Durham, NC 27708 USA
[2] Pittsburgh Supercomp Ctr, Pittsburgh, PA 15213 USA
关键词
D O I
10.1021/jp0132329
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The transition between single step long-range tunneling and multistep hopping transport in DNA electron transfer depends on a myriad of factors including sequence, distance, conformation, solvation and, consequently, hole state energetics. We show that the solvation energetics of hole (radical cation) states in DNA is comparable to the quantum delocalization energetics of the hole. That is, the solvation forces that tend to localize the hole compete with the quantum effects that give rise to hole delocalization. The net result is that the hole states are predicted to be relatively compact (one to three base pairs in length) and that the "trap depth" of these holes is expected to be much shallower than anticipated by gas-phase quantum chemical analysis of base stacks. This analysis predicts guanine oxidation potential dependence on the length of GC runs to be modest (differences < 0.1 V for holes from one to three base pairs). The lowering of the trapped hole binding energy has significant implications for the structure and mobility of hole states in DNA.
引用
收藏
页码:7 / 10
页数:4
相关论文
共 46 条
  • [1] Alexandrov A. S., 1995, POLARONS BIPOLARONS
  • [2] ATKINS PW, 1998, PHYSICAL CHEM
  • [3] On the long-range charge transfer in DNA
    Berlin, YA
    Burin, AL
    Ratner, MA
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (03) : 443 - 445
  • [4] Charge hopping in DNA
    Berlin, YA
    Burin, AL
    Ratner, MA
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (02) : 260 - 268
  • [5] ATOMIC CHARGES DERIVED FROM SEMIEMPIRICAL METHODS
    BESLER, BH
    MERZ, KM
    KOLLMAN, PA
    [J]. JOURNAL OF COMPUTATIONAL CHEMISTRY, 1990, 11 (04) : 431 - 439
  • [6] BEVERIDGE DL, 1991, THEORETICAL BIOCH MO
  • [7] Long-range charge hopping in DNA
    Bixon, M
    Giese, B
    Wessely, S
    Langenbacher, T
    Michel-Beyerle, ME
    Jortner, J
    [J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1999, 96 (21) : 11713 - 11716
  • [8] Case DA, 1999, AMBER 6
  • [9] Polarons in DNA
    Conwell, EM
    Rakhmanova, SV
    [J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2000, 97 (09) : 4556 - 4560
  • [10] A 2ND GENERATION FORCE-FIELD FOR THE SIMULATION OF PROTEINS, NUCLEIC-ACIDS, AND ORGANIC-MOLECULES
    CORNELL, WD
    CIEPLAK, P
    BAYLY, CI
    GOULD, IR
    MERZ, KM
    FERGUSON, DM
    SPELLMEYER, DC
    FOX, T
    CALDWELL, JW
    KOLLMAN, PA
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (19) : 5179 - 5197