HPr, a central component of the phosphoenolpyruvate-dependent phosphotransferase system, can exist in Escherichia coli in a phosphorylated (PHPr) and a nonphosphorylated form. We show that, beside the normal transfer of the phosphoryl group from PHPr to enzymes II and III, PHPr can phosphorylate other HPr molecules in an autocatalytic exchange reaction. The reaction is very fast but is inhibite...

Human ubiquitous mitochondrial creatine kinase (uMtCK) is responsible for the regulation of cellular energy metabolism. To investigate the phosphoryl-transfer mechanism catalyzed by human uMtCK, in this work, molecular dynamic simulations of uMtCK∙ATP-Mg2+∙creatine complex and quantum mechanism calculations were performed to make clear the puzzle. The theoretical studies hereof revealed that hu...

We have used vibrational spectroscopy to study bonding in monosubstituted dianionic phosphates, both to learn more about basic properties intrinsic to this important class of biological substrates and to assess the ability of vibrational spectroscopy to provide a "sensor" or probe of the local environment experienced by the phosphoryl group. We examined the bonding properties of the phosphoryl ...

PEP mutase catalyzes the conversion of phosphoenolpyruvate (PEP) to phosphonopyruvate in biosynthetic pathways leading to phosphonate secondary metabolites. A recent X-ray structure [Huang, K., Li, Z., Jia, Y., Dunaway-Mariano, D., and Herzberg, O. (1999) Structure (in press)] of the Mytilus edulis enzyme complexed with the Mg(II) cofactor and oxalate inhibitor reveals an alpha/beta-barrel back...

9-substituted adenine derivatives with protected phosphoryl groups were synthesized and tested as inhibitors of adenylyl cyclase in isolated enzyme and intact cell systems. Protected 3'-phosphoryl derivatives of 2',5'-dideoxyadenosine (2',5'-dd-Ado) and beta-l-2',5'-dd-Ado, protected 5'-phosphoryl derivatives of beta-l-2',3'-dd-Ado, and protected phosphoryl derivatives of two 9-(2-phosphonometh...

Enzyme I of the bacterial phosphoenolpyruvate: sugar phosphotransferase system catalyzes phosphoryl transfer from phosphoenolpyruvate to the heat-stable phosphoryl carrier protein, HPr. Enzyme I also catalyzes a rapid phosphoryl exchange reaction in which the phosphoryl moiety of phosphoenolpyruvate is transferred to pyruvate. Additionally, Enzyme I plus HPr catalyze the slow hydrolysis of pho...

Molecular probes are useful for both studying and controlling the functions of enzymes and other proteins. The most useful probes have high affinity for their target, along with small size and resistance to degradation. Here, we report on new surrogates for nucleic acids that fulfill these criteria. Isosteres in which phosphoryl [R-O-P(O(2)(-))-O-R'] groups are replaced with N-acylsulfonamidyl ...