Geometry of the Phosphate Group and Its Interactions with Metal Cations in Crystals and ab Initio Calculations

  title={Geometry of the Phosphate Group and Its Interactions with Metal Cations in Crystals and ab Initio Calculations},
  author={Bohdan Schneider and A. Kabelac and Pavel Hobza},
  journal={Journal of the American Chemical Society},
The phosphate geometry was studied in crystal environment by analyzing 178 crystal structures and in vacuo by ab initio calculations of (di)hydrogen and dimethyl phosphates and a diphosphate model system, CH3OP(O2)O(CH2)3OP(O2)OCH3 (diPh), at the MP2 and HF levels. Since charge determines the phosphate stereochemistry, uncharged, −1, and −2 phosphates were analyzed separately. The PO and OPO bonding parameters depend only on charge and the number of carbon substituents while the remaining… 

Computational study of dimethyl phosphate anion and its complexes with water, magnesium, and calcium

Dimethyl phosphate anion (DMP) is often used to simulate the properties of the phosphate group, an important structural fragment of nucleic acids and phospholipids. Besides its functional importance,

Effects of the Complexation by the Mg2+ Cation on the Stereochemistry of the Sugar−Diphosphate Linkage. Ab Initio Modeling on Nucleotide−Sugars

Ab initio molecular orbital calculations of the 2-O-methyldiphosphono-tetrahydropyran dianion (1) and the complex of magnesium with 2-O-methyldiphosphono-tetrahydropyran (2) are used to model the

Comparative DFT study on the α-glycosidic bond in reactive species of galactosyl diphosphates

Correct prediction of the structure and energetics along the reaction pathway of the formation or dissociation of the glycosidic bond in sugar phosphates is crucial for the understanding of catalytic

The influence of square planar platinum complexes on DNA base pairing. An ab initio DFT study

The energetics and structures of guaninecytosine (GC) and adeninethymine (AT) Watson–Crick base pairs metalated by the square planar platinum adducts trans-PtCl2(NH3), trans-PtCl(NH3)2+ and

Crystal structure and molecular stereochemistry of polymeric Cu2(DMP)4(DMSO) as a platform for phosphate diester binding

Treatment of a solution of CuCl2 in dimethyl phosphate (DMP) in an inert solvent under nitrogen atmosphere resulted in a light blue fluorescence powder. Slow evaporation of H2O‐DMSO solution of this

Structure and binding of Mg(II) ions and di-metal bridge complexes with biological phosphates and phosphoranes

The results presented here provide quantitative characterization of metal ion binding to ligands of importance to RNA catalysis, and lay the groundwork for design of new generation quantum models that can be applied to the full biological enzymatic systems.


Phosphorus-31 NMR : principles and applications

This work focuses on the application of Phosphorus-31 NMR to Biochemistry in the context of Enzymatic Phosphoryl Transfer Reactions, and the theory and application of Relaxation Behavior of Nucleic Acids and Phosphoproteins.