Enzymatic Synthesis of Nucleoside Triphosphates. Does It Involve An Ion-Radical Path ?
DOI:
https://doi.org/10.24297/jac.v4i3.950Keywords:
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
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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
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