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Structural characterization of a carbon monoxide adduct of a heme–DNA complex
- Source :
- JBIC Journal of Biological Inorganic Chemistry. 17:437-445
- Publication Year :
- 2011
- Publisher :
- Springer Science and Business Media LLC, 2011.
-
Abstract
- The structure of a carbon monoxide (CO) adduct of a complex between heme and a parallel G-quadruplex DNA formed from a single repeat sequence of the human telomere, d(TTAGGG), has been characterized using ¹H and ¹³C NMR spectroscopy and density function theory calculations. The study revealed that the heme binds to the 3'-terminal G-quartet of the DNA though a π-π stacking interaction between the porphyrin moiety of the heme and the G-quartet. The π-π stacking interaction between the pseudo-C₂-symmetric heme and the C₄-symmetric G-quartet in the complex resulted in the formation of two isomers possessing heme orientations differing by 180° rotation about the pseudo-C₂ axis with respect to the DNA. These two slowly interconverting heme orientational isomers were formed in a ratio of approximately 1:1, reflecting that their thermodynamic stabilities are identical. Exogenous CO is coordinated to heme Fe on the side of the heme opposite the G-quartet in the complex, and the nature of the Fe-CO bond in the complex is similar to that of the Fe-CO bonds in hemoproteins. These findings provide novel insights for the design of novel DNA enzymes possessing metalloporphyrins as prosthetic groups.
- Subjects :
- Models, Molecular
Carbon Monoxide
Magnetic Resonance Spectroscopy
Hemeprotein
Molecular Structure
biology
Stereochemistry
DNA
Heme
Nuclear magnetic resonance spectroscopy
Biochemistry
Porphyrin
Cofactor
Adduct
G-Quadruplexes
Inorganic Chemistry
chemistry.chemical_compound
chemistry
biology.protein
Humans
Quantum Theory
Molecule
Organic chemistry
Carbon monoxide
Subjects
Details
- ISSN :
- 14321327 and 09498257
- Volume :
- 17
- Database :
- OpenAIRE
- Journal :
- JBIC Journal of Biological Inorganic Chemistry
- Accession number :
- edsair.doi.dedup.....23a96b33b4e05ffc7a17ab599ca09457