An electronic effect on protein structure

被引:236
作者
Hinderaker, MP
Raines, RT
机构
[1] Univ Wisconsin, Dept Biochem, Madison, WI 53706 USA
[2] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA
关键词
Burgi-Dunitz trajectory; collagen; hyperconjugation; peptide bond; polyproline II helix; proline isomerization; stereoelectronic effect; steric effect;
D O I
10.1110/ps.0241903
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The well-known preference of the peptide bond for the trans conformation has been attributed to steric effects. Here, we show that a proline residue with an N-formyl group (Hi-1-Ci-1' = Oi-1), in which Hi-1 presents less steric hindrance than does Oi-1, likewise prefers a trans conformation. Thus, the preference of the peptide bond for the trans conformation cannot be explained by steric effects alone. Rather, an n --> pi* interaction between the oxygen of the peptide bond (Oi-1), and the subsequent carbonyl carbon in the polypeptide chain (C-i') also contributes to this preference. The Oi-1 and C-i' distance and Oi-1...C-i' = O-i angle are especially favorable for such an n --> pi* interaction in a polyproline II helix. We propose that this electronic effect provides substantial stabilization to this and other elements of protein structure.
引用
收藏
页码:1188 / 1194
页数:7
相关论文
共 66 条
[1]   Retention of the cis proline conformation in tripeptide fragments of bovine pancreatic ribonuclease A containing a non-natural proline analogue, 5,5-dimethylproline [J].
An, SSA ;
Lester, CC ;
Peng, JL ;
Li, YJ ;
Rothwarf, DM ;
Welker, E ;
Thannhauser, TW ;
Zhang, LS ;
Tam, JP ;
Scheraga, HA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (49) :11558-11566
[2]   Bactericidal activity and poly-L-proline II conformation of the tandem repeat sequence of human salivary mucin glycoprotein (MG2) [J].
Antonyraj, KJ ;
Karunakaran, T ;
Raj, PA .
ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS, 1998, 356 (02) :197-206
[3]  
BALDWIN JE, 1976, CHEM COMMUN, P738
[4]   CRYSTAL-STRUCTURE AND MOLECULAR-STRUCTURE OF A COLLAGEN-LIKE PEPTIDE AT 1.9-ANGSTROM RESOLUTION [J].
BELLA, J ;
EATON, M ;
BRODSKY, B ;
BERMAN, HM .
SCIENCE, 1994, 266 (5182) :75-81
[5]   Quantum mechanical study of the conformational behavior of proline and 4R-hydroxyproline dipeptide analogues in vacuum and in aqueous solution [J].
Benzi, C ;
Improta, R ;
Scalmani, G ;
Barone, V .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 2002, 23 (03) :341-350
[6]   Visualization of solvation structures in liquid mixtures [J].
Bergman, DL ;
Laaksonen, L ;
Laaksonen, A .
JOURNAL OF MOLECULAR GRAPHICS & MODELLING, 1997, 15 (05) :301-+
[7]   EXPERIMENTS TOWARDS THE SYNTHESIS OF CORRINS .1. THE PREPARATION AND REACTIONS OF SOME DELTA-1- PYRROLINES - A NOVEL PROLINE SYNTHESIS [J].
BONNETT, R ;
CLARK, VM ;
GIDDEY, A ;
TODD, A .
JOURNAL OF THE CHEMICAL SOCIETY, 1959, (JUN) :2087-2093
[8]   The crystal and liquid structures of N,N-dimethylthioformamide and N,N-dimethylformamide showing a stronger hydrogen bonding effect for C-H•••S than for C-H•••O [J].
Borrmann, H ;
Persson, I ;
Sandström, M ;
Stålhandske, CMV .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 2000, (02) :393-402
[9]   Conformational stability of collagen relies on a stereoelectronic effect [J].
Bretscher, LE ;
Jenkins, CL ;
Taylor, KM ;
DeRider, ML ;
Raines, RT .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (04) :777-778
[10]   FROM CRYSTAL STATICS TO CHEMICAL-DYNAMICS [J].
BURGI, HB ;
DUNITZ, JD .
ACCOUNTS OF CHEMICAL RESEARCH, 1983, 16 (05) :153-161