Details

Autor(en) / Beteiligte

• Zolotarev, Yurii A
• Dadayan, Alexander K
• Borisov, Yurii A
• Kozik, Valery S
• Nazimov, Igor V
• Ziganshin, Rustam H
• Bocharov, Eduard V
• Chizhov, Alexander O
• Myasoedov, Nikolay F

Titel

New Development in the Solid-State Isotope Exchange with Spillover Hydrogen in Organic Compounds

Ist Teil von

• Journal of physical chemistry. C, 2013-08, Vol.117 (33), p.16878-16884

Ort / Verlag

American Chemical Society

Erscheinungsjahr

2013

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Solid-state catalytic isotope exchange of hydrogen under the action of spillover hydrogen in organic compounds applied on a nonorganic carrier has been studied. The deuterium-labeled peptide [D]dalargin containing 14 deuterium atoms, [D]melatonin, and [D]histamine with the 72–92% substitution degree of all C–H bonds were prepared by this reaction. The activation energy of hydrogen isotope exchange with T2 and D2 in glycine and α-aminoisobutyric acid was obtained experimentally. It was shown that for the studied reaction the kinetic isotopic effect is 1.2–1.4 by the Hartree–Fock method, which is several times smaller than one in the liquid-phase reactions. Quantum chemical calculations of the isotope shift values in the electronic spectra of deuterium-labeled metal ion complexes were performed using the RB3LYP/LanL2DZ and CIS/LanL2DZ methods for calculation of the ground and the excited states. It was shown for deuterium-labeled histamine complexes [D12]Pd(him)2Cl2 and [D12]Cu(him)2Cl that the isotopic effect of UV spectra was 1600 and 1800 cal/mol, respectively. The measurement of isotopic shifts for electronic transitions potentially can be utilized as a new informative method for the investigation of complex formation. The deuterium-labeled compounds were shown to be useful as internal standards for quantitative mass spectroscopy (MS) analysis.