Phosphoryl-transfer reactions phosphorylated

FIGURE 3.8 The activation energies for phosphoryl group-transfer reactions (200 to 400 kj/mol) are substantially larger than the free energy of hydrolysis of ATP ( — 30.5 kj/mol). 

The role of divalent cations in the mechanism of enzyme catalysed phosphoryl and nucleotidyl transfer reactions. A. S. Mildvan and C. M. Grisham, Struct. Bonding (Berlin), 1974,20,1-21 (88),... 

HYBRID POTENTIALS FOR THE SIMULATION OF PHOSPHORYL TRANSFER REACTIONS... 

The AMl/d-PhoT model [33] is a parameterization of a modified AMl/d Hamiltonian developed specifically to model phosphoryl transfer reactions catalyzed by enzymes and ribozymes for use in linear-scaling calculations and combined QM/MM simulations. The model is currently parametrized for H, O, and P atoms to reproduce... 

Smooth COSMO solvation model. We have recently extended our smooth COSMO solvation model with analytical gradients [71] to work with semiempirical QM and QM/MM methods within the CHARMM and MNDO programs [72, 73], The method is a considerably more stable implementation of the conventional COSMO method for geometry optimizations, transition state searches and potential energy surfaces [72], The method was applied to study dissociative phosphoryl transfer reactions [40], and native and thio-substituted transphosphorylation reactions [73] and compared with density-functional and hybrid QM/MM calculation results. The smooth COSMO method can be formulated as a linear-scaling Green s function approach [72] and was applied to ascertain the contribution of phosphate-phosphate repulsions in linear and bent-form DNA models based on the crystallographic structure of a full turn of DNA in a nucleosome core particle [74],... 

Case Study Comparison of DFT Functionals on Model Phosphoryl Transfer Reactions... 

Mechanistically it was proposed that the substrate bridges both Zn(II) ions and replaces the apical amines in 28 while one of them attacks the phosphorus atom as an intramolecular nucleophile to perform the phosphoryl-transfer reaction (30). The presented observations are not re-... 

In every type of biological phosphoryl transfer reaction, a P-O bond of the leaving group (R2-OH) is broken and a new P-O bond is formed between phosphorus and the attacking group R -OH ... 

Aside from being fundamentally interesting and industrially important, phosphoryl and acyl transfer reactions are key biological processes. Numerous enzymes con-... 

Magnesium has its role intimately intertwined with phosphate in many phosphoryl transfer reactions, as Mg-ATP in muscle contraction, in the stabilization of nucleic acid structures as well as in the catalytic activity of ribozymes (catalytic RNA molecules). It also serves as a structural component of enzymes, and is found as the metal centre in chlorophylls, which absorbs light energy in photosynthesis. 

Phosphoryl group transfer reactions add or remove phosphoryl groups to or from cellular metabolites and macromolecules, and play a major role in biochemistry. Phosphoryl transfer is the most common enzymatic function coded by the yeast genome and, in addition to its importance in intermediary metabolism (see Chapter 5), the reaction is catalysed by a large number of central regulatory enzymes that are often part of signalling cascades, such as protein kinases, protein phosphatases, ATPases and GTPases. 

Figure 10.3 In the phosphoryl-transfer reaction catalysed by hexokinase, the y-phosphoryl group of ATP undergoes inversion of configuration. (From Voet and Voet, 2004. Reproduced with permission from John Wiley Sons., Inc.)...

Figure 10.8 The phosphoglucomutase reaction proceeds via two phosphoryl-transfer reactions. (From Allen and Dunaway-Mariano, 2004. Copyright 2004, with permission from Elsevier.)...

Figure 10.13 Phosphoryl-transfer reactions. The figure shows (a) nucleotide polymerization, (b) nucleic acid hydrolysis, (c) first cleavage of an exon-intron junction by group I ribozyme (d) and by a group II ribozyme, (e) strand transfer during transposition and (f) exon ligation during RNA splicing. (From Yang et al., 2006. Copyright 2006, with permission from Elsevier.)...

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