Quantum chemical evaluation of protein control over heme ligation:: CO/O2 discrimination in myoglobin

被引:46
作者
De Angelis, F [1 ]
Jarzecki, AA [1 ]
Car, R [1 ]
Spiro, TG [1 ]
机构
[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA
关键词
D O I
10.1021/jp0451851
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
Control of O-2 versus CO binding in myoglobin (Mb) is tuned by a distal histidine residue through steric and H-bonding interactions. These interactions have been evaluated via Car-Parrinello DFT calculations, whose efficiency allows full quantum mechanical treatment of the 13 closest residues surrounding the heme. The small (8degrees) deviation of the Fe-C-O bond angle from linearity results from the steric influence of a distal valine residue and not the distal histidine. H-bond energies were evaluated by replacing the distal histidine with the non-H-bonding residue isoleucine. Binding energies for CO and O-2 decreased by 0.8 and 4.1 kcal/mol for MbCO and MbO(2), in good agreement with experimental H-bond estimates. Ligand discrimination is dominated by distal histidine H-bonding, which is also found to stabilize a metastable side-on isomer of MbO(2) that may play a key role in MbO(2) photodynamics.
引用
收藏
页码:3065 / 3070
页数:6
相关论文
共 67 条
[1]   Unexpectedly large basis set effects on the binding of O2 to heme complexes [J].
Barea, G ;
Maseras, F ;
Lledós, A .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2001, 85 (02) :100-108
[2]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[3]  
BERTRAN J, 1991, J MOL STRUC-THEOCHEM, V78, P337, DOI 10.1016/0166-1280(91)85263-7
[4]   UNIFIED APPROACH FOR MOLECULAR-DYNAMICS AND DENSITY-FUNCTIONAL THEORY [J].
CAR, R ;
PARRINELLO, M .
PHYSICAL REVIEW LETTERS, 1985, 55 (22) :2471-2474
[5]   O-2 AND CO REACTIONS WITH HEME-PROTEINS - QUANTUM YIELDS AND GEMINATE RECOMBINATION ON PICOSECOND TIME SCALES [J].
CHANCE, MR ;
COURTNEY, SH ;
CHAVEZ, MD ;
ONDRIAS, MR ;
FRIEDMAN, JM .
BIOCHEMISTRY, 1990, 29 (23) :5537-5545
[6]   HYDRATION IN PROTEIN CRYSTALS - A NEUTRON-DIFFRACTION ANALYSIS OF CARBONMONOXYMYOGLOBIN [J].
CHENG, XD ;
SCHOENBORN, BP .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1990, 46 :195-&
[7]   Synthetic models for hemoglobin and myoglobin [J].
Collman, JP ;
Fu, L .
ACCOUNTS OF CHEMICAL RESEARCH, 1999, 32 (06) :455-463
[8]   Molecular structure and conformation of dinitrosylheme [J].
Conradie, J ;
Wondimagegn, T ;
Ghosh, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (17) :4968-4969
[9]   Molecular properties from combined QM/MM methods. I. Analytical second derivative and vibrational calculations [J].
Cui, Q ;
Karplus, M .
JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (03) :1133-1149
[10]   Role of ligand bending in the photodissociation of O2 vs CO-heme:: A time-dependent density functional study [J].
De Angelis, F ;
Car, R ;
Spiro, TG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (51) :15710-15711