Mechanistic alternatives in phosphate monoester hydrolysis: what conclusions can be drawn from available experimental data?

Phosphate monoester hydrolysis reactions in enzymes and solution are often discussed in terms of whether the reaction pathway is associative or dissociative. Although experimental results for solution reactions have usually been considered as evidence for the second alternative, a closer thermodynamic analysis of observed linear free energy relationships shows that experimental information is consistent with the associative, concerted and dissociative alternatives.

[1]  Secondary 18O isotope effects on the hydrolysis of glucose 6-phosphate , 1986 .

[2]  M. Younas,et al.  The reactivity of phosphate esters. Reactions of diesters with nucleophiles , 1970 .

[3]  A. J. Kirby,et al.  The Reactivity of Phosphate Esters. Monoester Hydrolysis , 1967 .

[4]  G Schneider,et al.  Crystal structures of rat acid phosphatase complexed with the transition-state analogs vanadate and molybdate. Implications for the reaction mechanism. , 1994, European journal of biochemistry.

[5]  M Geyer,et al.  Linear free energy relationships in the intrinsic and GTPase activating protein-stimulated guanosine 5'-triphosphate hydrolysis of p21ras. , 1996, Biochemistry.

[6]  E. Magid,et al.  The rates of the spontaneous hydration of CO2 and the reciprocal reaction in neutral aqueous solutions between 0° and 38° , 1968 .

[7]  A. Warshel,et al.  Phosphate Ester Hydrolysis in Aqueous Solution: Associative versus Dissociative Mechanisms , 1998 .

[8]  A. Warshel,et al.  Computer simulations of enzymatic reactions: examination of linear free-energy relationships and quantum-mechanical corrections in the initial proton-transfer step of carbonic anhydrase. , 1992, Faraday discussions.

[9]  A. Hengge,et al.  Transition-State Structures for Phosphoryl- TransferReactions of p-Nitrophenyl Phosphate , 1994 .

[10]  P R Evans,et al.  Phosphofructokinase: structure and control. , 1981 .

[11]  W. Jencks,et al.  Mechanism and Catalysis of Reactions of Acyl Phosphates. II. Hydrolysis1 , 1961 .

[12]  Arieh Warshel,et al.  LINEAR FREE ENERGY RELATIONSHIPS IN ENZYMES. THEORETICAL ANALYSIS OF THE REACTION OF TYROSYL-TRNA SYNTHETASE , 1994 .

[13]  L. Pearson,et al.  The kinetics of combination of carbon dioxide with hydroxide ions , 1956 .

[14]  A. Warshel,et al.  Mechanistic analysis of the observed linear free energy relationships in p21ras and related systems. , 1996, Biochemistry.

[15]  H. Hamm,et al.  GTPase mechanism of Gproteins from the 1.7-Å crystal structure of transducin α - GDP AIF−4 , 1994, Nature.

[16]  W. Jencks,et al.  Phosphoryl transfer between pyridines , 1983 .

[17]  D. Herschlag,et al.  Evidence that metaphosphate monoanion is not an intermediate in solvolysis reactions in aqueous solution , 1989 .

[18]  Determination of equilibrium 18O isotope effects on the deprotonation of phosphate and phosphate esters and the anomeric effect on deprotonation of glucose 6-phosphate , 1986 .

[19]  A. Warshel,et al.  On the Reactivity of Phosphate Monoester Dianions in Aqueous Solution: Brønsted Linear Free-Energy Relationships Do Not Have an Unique Mechanistic Interpretation , 1998 .

[20]  D. Herschlag,et al.  Mapping the transition state for ATP hydrolysis: implications for enzymatic catalysis. , 1995, Chemistry & biology.

[21]  S. Benkovic,et al.  6 Chemical Basis of Biological Phosphoryl Transfer , 1973 .

[22]  D. R. Llewellyn,et al.  716. The reactions of organic phosphates. Part I. The hydrolysis of methyl dihydrogen phosphate , 1958 .

[23]  D. Herschlag,et al.  Ras-catalyzed hydrolysis of GTP: a new perspective from model studies. , 1996, Proceedings of the National Academy of Sciences of the United States of America.

[24]  E. E. Kim,et al.  Reaction mechanism of alkaline phosphatase based on crystal structures. Two-metal ion catalysis. , 1991, Journal of molecular biology.

[25]  Arieh Warshel,et al.  Simulation of enzyme reactions using valence bond force fields and other hybrid quantum/classical approaches , 1993 .

[26]  A V Finkelstein,et al.  The price of lost freedom: entropy of bimolecular complex formation. , 1989, Protein engineering.

[27]  J. Guthrie.  Hydration and dehydration of phosphoric acid derivatives: free energies of formation of the pentacoordinate intermediates for phosphate ester hydrolysis and of monomeric metaphosphate , 1977 .

[28]  B. Silver,et al.  Reactions of organic phosphates. Part VI. The hydrolysis of aryl phosphates , 1966 .

[29]  F. Westheimer,et al.  The Lanthanum Hydroxide Gel Promoted Hydrolysis of Phosphate Esters , 1955 .

[30]  R. Wolfenden,et al.  Spontaneous Hydrolysis of Ionized Phosphate Monoesters and Diesters and the Proficiencies of Phosphatases and Phosphodiesterases as Catalysts , 1998 .

[31]  W. Kabsch,et al.  The Ras-RasGAP complex: structural basis for GTPase activation and its loss in oncogenic Ras mutants. , 1997, Science.

[32]  W. Cleland,et al.  Alkaline phosphatase catalyzes the hydrolysis of glucose-6-phosphate via a dissociative mechanism , 1989 .

[33]  Donald G. Truhlar,et al.  AM1-SM2 and PM3-SM3 parameterized SCF solvation models for free energies in aqueous solution , 1992, J. Comput. Aided Mol. Des..

[34]  A. Warshel,et al.  A Fundamental Assumption about OH- Attack in Phosphate Ester Hydrolysis Is Not Fully Justified , 1997 .

[35]  R. C. Weast.  CRC Handbook of Chemistry and Physics , 1973 .

[36]  R. Fröhlich,et al.  Mechanism of Fe(III)-Zn(II) purple acid phosphatase based on crystal structures. , 1996, Journal of molecular biology.

[37]  J. Dunitz.  The entropic cost of bound water in crystals and biomolecules. , 1994, Science.