Study of the Activation Process of Isotope Exchange between Boc-Trp-Pro-Pro-Trp, Trp-Pro-Pro-Trp and Deuterated Water

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Abstract

The conditions for introducing deuterium into Trp-Pro-Pro-Trp and Boc-Trp-Pro-Pro-Trp by isotope exchange with D2O in the presence of a 5% Pd/Al2O3 catalyst were developed. The thermal stability of Trp-Pro-Pro-Trp upon introduction of deuterium was significantly lower than that of the Boc-protected peptide. The yield of deuterated Trp-Pro-Pro-Trp did not exceed 10–15%, and the inclusion of deuterium was about 0.9–1.1 at./molecule at 125°C. The introduction of deuterium into Boc-Trp-Pro-Pro-Trp was possible at 150°C, which increased the deuterium content to 3.75 at./molecule. It was found that the tryptophan fragment of the molecule contains approximately 2 times more deuterium than the proline fragment. It was found that pretreatment of Boc-Trp-Pro-Pro-Trp with deuterium gas not only activates isotope exchange, but also promotes the removal of Boc protection. The data obtained indicate that the reason for this phenomenon is associated with the generation of deuterium cations on Boc-Trp-Pro-Pro-Trp molecules by the catalyst.

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V. P. Shevchenko

National Research Centre Kurchatov Institute

Author for correspondence.
Email: nagaev.img@yandex.ru
Russian Federation, pl. Kurchatova 2, Moscow, 123182

K. V. Shevchenko

National Research Centre Kurchatov Institute

Email: nagaev.img@yandex.ru
Russian Federation, pl. Kurchatova 2, Moscow, 123182

I. Y. Nagaev

National Research Centre Kurchatov Institute

Email: nagaev.img@yandex.ru
Russian Federation, pl. Kurchatova 2, Moscow, 123182

L. A. Andreeva

National Research Centre Kurchatov Institute

Email: nagaev.img@yandex.ru
Russian Federation, pl. Kurchatova 2, Moscow, 123182

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2. Fig.

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3. Scheme 1. The introduction of deuterium into polyunsaturated fatty acids.

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4. 1. Peptide isotopomers formed during treatment of the Boc-Trp-Pro-Pro-Trp-5% Pd/Al2O3–Al2O3 mixture (1 :5 : 30): (a) D2 (solid-phase method), 170°C; (b) D2O (liquid-phase method), 150°C.

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5. 2. Peptide isotopomers formed during isotopic exchange with D2O after pretreatment of the D2 mixture Boc-Trp-Pro-Pro-Trp-5% Pd/Al2O3–Al2O3 (1 : 5 : 30).

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