It is proposed that enzymic phosphoryl-transfer reactions occur by concerted, step-wise, associative (phosphorane-intermediate) or dissociative (metaphosphate-intermediate) mechanisms, as dictated by the catalytic scaffold and the reactants. During the evolution of a phosphotransferase family, the mechanism of the phosphoryl-transfer reaction is in constant flux, potentially changing with each ...

The variable mechanism for substitution of P-stereogenic phosphoryl chloride with alkynyl metallic reagents, which depends on temperature, stoichiometry of starting materials, and the structure of the nucleophilic reagent, is assumed as either SN2-like or Berry pseudorotation of pentacoordinated phosphorus intermediates, affording inversion and retention products, respectively. The formation of...

Rabbit muscle phosphoglucomutase converts a-D-glucose 1_[(S)-160,17O,8Olphosphate into D-glucose 6-[160,'70,18Olphosphate, which is shown by 31P n.m.r. spectroscopy, after cyclization and methylation, to have the (S)-configuration at the phosphorus atom. Since phosphoglucomutase is known to catalyse phosphoryl transfer by way of a phospho-enzyme intermediate, and since individual phosphoryl-tra...

Purified phosphoryl transferase catalyzes an ATP-ADP exchange reaction. Evidence is presented which excludes the possibility that the exchange activity of the preparation is due to contaminating adenylate kinase. The rate of the exchange reaction is affected by the molar ratio of ATP to ADP. The reaction is not highly specific either for the divalent metal ion or for the nucleoside triphosphate...

Boron neutron capture therapy (BNCT) is a chemoradio-therapeutic method for the treatment of cancer. It depends on the selective targeting of tumor cells by boron-containing compounds. One category of BNCT agents with potential to selectively target tumor cells may be thymidine derivatives substituted at the 3'-position with appropriate boron moieties. Thus, several thymidine analogues were syn...

Phosphoryl transfer reactions figure prominently in energy metabolism, signaling, transport and motility. Prior detailed studies of selected systems have highlighted mechanistic features that distinguish different phosphoryl transfer enzymes. Here, a top-down approach is developed for comparing statistically the active site configurations between populations of diverse structures in the Protein...

The formation of transition state mimics of phosphoryl transfer reactions with the metal oxoanion vanadate is a powerful technique in macromolecular crystallography. The tendency of vanadate to form pentacovalent complexes exhibiting trigonal bipyramidal geometry makes this compound a close approximation of the transition state for such reactions. In many cases, vanadate complexes provide the m...

The reversible conversion of 3-phosphoryl-n-glyceric acid (3PGA) into 2-phosphoryl-n-glyceric acid (2PGA) was first shown to occur in rabbit muscle extracts by Meyerhof and Kiessling (1) as one step in the pathway of glycolysis. These authors determined an equilibrium constant for this reaction in crude muscle extracts and showed that only the D(-) isomers of 2PGA and 3PGA were substrates. Alth...

Phosphoryl transfer from the high-energy phosphate donor ATP is ubiquitous in biological chemistry, and nitrogen nucleophiles, especially histidine, often serve as in vivo acceptors of the γ-phosphate of ATP. Nevertheless, nonenzymatic reactions of ATP with amines have not previously been characterized. We have therefore examined phosphoryl transfer from ATP to amines to provide a basis for und...