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A Thermodynamic and Kinetic Study on the Stability of the Conformational States of N-Acetyl-proline-methylamide by IR. spectroscopy and chemical relaxation

✍ Scribed by Rudolf Hopmann


Publisher
John Wiley and Sons
Year
1974
Tongue
German
Weight
360 KB
Volume
57
Category
Article
ISSN
0018-019X

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✦ Synopsis


Abstract

N‐Acetyl‐proline‐methylamide (APMA) was synthesized by the mixed anhydride method and investigated by IR. spectroscopy and chemical relaxation measurements. The temperature‐induced variation of the IR. absorption bands of the internally hydrogen bonded (b) and of the extended, unbonded (e) species at 3330 and 3450 cm^−1^ respectively, were used to evaluate the molar absorptivities, a(b) = 280 and a(e) = 50 l/mol · cm, the equilibrium constant K = 0.70, and the molar enthalpy of reaction Δ__H__ = − 2280 ± 60 cal/mol. The entropy was estimated to be in the range − 8 to − 9 e.u. The reaction rates of this conformational transition were measured by the chemical dipole field effect. The relaxation time of the rate process is τ = 2.7 · 10^−9^s, the rate constant for the formation of the hydrogen bond k(b) is 2.2 · 10^8^ s^−1^, and that for the unfolding accompanied by the breakage of the amide hydrogen bond k(e) is 1.5 · 10^8^s^−1^.