Enzymatic Synthesis of Nucleoside Triphosphates. Does It Involve An Ion-Radical Path ?

Authors

  • Anatoly L. Buchachenko N. N. Semenov Institute for Chemical Physics, Russian Academy of Sciences, Moscow 119991
  • Maxim E. Grigoryev N. I. Pirogov Russian National Research Medical University, Russian Federal Ministry of Health, Moscow 117997
  • Natalya N. Breslavskaya N. S .Kurnakov Institute for General and Inorganic Chemistry, Russian Academy of Sciences, Moscow119991
  • Dmitry A. Kuznetsov N. N. Semenov Institute for Chemical Physics, Russian Academy of Sciences, Moscow 119991, Russia N. I. Pirogov Russian National Research Medical University, Russian Federal Ministry of Health, Moscow 117997, Russia

DOI:

https://doi.org/10.24297/jac.v4i3.950

Keywords:

Mass-independent isotope effect, magnetic isotope effect, ion-radical pairs, singlet – triplet spin conversion, Coulomb hyperfine coupling, enzymatic phosphorylation, magnesium isotopes.

Abstract

Accumulation and release of energy in the nucleoside triphosphate enzymatic synthesis and hydrolysis does not limited to a routine energy consuming nucleophilic mechanism. These processes require an overcoming the large energy barrier exceeding a total value of accumulated or released energy level by at least 3 – 4 times (~10 kcal/mol). This energy is supposed to be taken from the mechanical compression of the catalytic site and used to form P–O chemical bond by a direct nucleophilic addition of phosphate to nucleoside diphosphate (ADP as an example). A new, energetically “cheapâ€, ion-radical mechanism of the ATP biosynthesis has been proposed due to the observation of magnetic isotope and magnetic field effects on the ATP synthesis. This mechanism is about to generate  a compression energy to “spend†on a partial dehydratation of magnesium ion inside the nucleotidyl transferase catalyric site (energy cost of this process is 3-5 kcal/mol, i.e. by 2-3 times less than a total accumulated or released energy). Dehydration of this ion is to increase its electron affinity and hence to stimulate an electron transfer from ADP3- to Mg2+. This reaction is a starting point of the ion-radical mechanism considering the molecular mechanics of enzymatic machines and its quantum chemistry background as well. To the contrast of a hardly controllable nucleophilic path, the ion-radical mechanism might be turned on/off  by a targeted delivery of  paramagnetic magnesium ions, 25Mg2+, towards the phosphate transferring enzyme catalytic site. The magnesium isotope substitution is easily reachable by the endo-osmotic pressure techniques, which makes it attractive for further biotechnological and/or pharmacological application(s).

Downloads

Download data is not yet available.

Downloads

Published

2008-12-12

How to Cite

Buchachenko, A. L., Grigoryev, M. E., Breslavskaya, N. N., & Kuznetsov, D. A. (2008). Enzymatic Synthesis of Nucleoside Triphosphates. Does It Involve An Ion-Radical Path ?. JOURNAL OF ADVANCES IN CHEMISTRY, 4(3), 525–531. https://doi.org/10.24297/jac.v4i3.950

Issue

Section

Articles