Study of solid-state catalytic isotope exchange of hydrogen inl-hydroxyproline under the action of spillover tritium |
| |
Authors: | Yu A Zolotarev Yu A Borisov |
| |
Institution: | (1) Institute of Molecular Genetics, Russian Academy of Sciences, 26 pl. Kurchatova, 123182 Moscow, Russian Federation;(2) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813 Moscow, Russian Federation |
| |
Abstract: | Reaction of high-temperature solid-state catalytic isotope exchange (HSCIE) of hydrogen in L-hydroxyproline was studied byab initio quantum-chemical calculations. A one-center synchronous mechanism of isotope exchange between the amino acid and the H3O+ model acidic center was considered. The structures of transition states of the reaction and the activation energies were
determined. Relative reactivity of the C−H bonds in the hydroxyproline molecule under conditions of HSCIE was studied. The
results obtained are in agreement with experimental data on the stereoselectivity and regioselectivity of the HSCIE reaction,viz., the lower the calculated activation energy of isotope exchange, the larger the portion of hydrogen substituted by tritium
in a given position of the amino acid molecule. The enhancement of the reactivity under conditions of solid-state isotope
exchange can be associated with additional interaction between the exchanging H atoms and the electron-donor O and N atoms
of the amino acid molecule in transition state.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1056–1060, June, 1999. |
| |
Keywords: | ab initio quantum-chemical calculations activation energy hydrogen isotope exchange hydrogen spillover |
本文献已被 SpringerLink 等数据库收录! |
|