Cooperative hydrogen-bonding in adenine-thymine and guanine-cytosine base pairs. Density functional theory and Moller-Plesset molecular orbital study

被引:174
作者
Asensio, A
Kobko, N
Dannenberg, JJ
机构
[1] CUNY Hunter Coll, Dept Chem, New York, NY 10021 USA
[2] Grad Sch, New York, NY 10021 USA
关键词
D O I
10.1021/jp0344646
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 cooperative contributions to the H-bonding interaction energies of the adenine-thymine and guanine-cytosine base pairs have been evaluated using molecular orbital theory. The energies of the individual bonds in each base pair were ascertained by using models structures that keep one H-bond at a time intact by rotating, one base with respect to the other about the axis of each H-bond to form structures with the bases perpendicular to each other. The energies of the individual H-bonds calculated in this way are compared with those of the planar base pairs. Optimized geometries were obtained using ab initio molecular orbital theory with electron correlation (MP2/D95**) and density functional theory (B3LYP/D95**). The cooperative contributions are of similar magnitude for each base pair. However, since the A-T overall interaction is weaker, the cooperative interaction provides 31% of its stability versus only 12-16% for G.C. The relatively smaller cooperative contribution to G.C is due to the difficulty of forming three optimal H-bonds between two rigid molecules. Structural modifications that might strengthen one H-bond tend to weaken another. As a result the central H-bond of G.C appears to be compressed by the attractive interaction in the two outer H-bonds. To the extent that these observations can be generalized, they should be important to the design of materials that utilize H-bonding motifs for self-assembly.
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页码:6441 / 6443
页数:3
相关论文
共 34 条
[1]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[2]  
Belosludov R. V., 1999, MOL ENG, V8, P105
[3]   Distance dependent hydrogen bond potentials for nucleic acid base pairs from ab initio quantum mechanical calculations (LMP2/cc-pVTZ) [J].
Brameld, K ;
Dasgupta, S ;
Goddard, WA .
JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (24) :4851-4859
[4]   Ab initio quantum mechanical study of the structures and energies for the pseudorotation of 5′-dehydroxy analogues of 2′-deoxyribose and ribose sugars [J].
Brameld, KA ;
Goddard, WA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (05) :985-993
[5]   STUDY OF ELECTRONIC STRUCTURE OF MOLECULES .12. HYDROGEN BRIDGES IN GUANINE-CYTOSINE PAIR AND IN DIMERIC FORM OF FORMIC ACID [J].
CLEMENTI, E ;
MEHL, J ;
VONNIESS.W .
JOURNAL OF CHEMICAL PHYSICS, 1971, 54 (02) :508-&
[6]   Hydrogen-bond acid/base catalysis: A density functional theory study of protonated guanine-(substituted) cytosine base pairs as models for nucleophilic attack on mitomycin in DNA [J].
Dannenberg, JJ ;
Tomasz, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (09) :2062-2068
[7]   ABINITIO APPROACH TO MOLECULAR-CRYSTALS - A PERIODIC HARTREE-FOCK STUDY OF CRYSTALLINE UREA [J].
DOVESI, R ;
CAUSA, M ;
ORLANDO, R ;
ROETTI, C ;
SAUNDERS, VR .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (12) :7402-7411
[8]  
Frisch M.J., 1998, GAUSSIAN 98
[9]   THEORETICAL INVESTIGATION OF THE HYDROGEN-BOND STRENGTHS IN GUANINE CYTOSINE AND ADENINE THYMINE BASE-PAIRS [J].
GOULD, IR ;
KOLLMAN, PA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (06) :2493-2499
[10]  
Guerra CF, 2000, J AM CHEM SOC, V122, P4117