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The effect of adjacent charges on the kinetics of rotation of the peptide bond

โœ Scribed by J. T. Gerig

Publisher
Wiley (John Wiley & Sons)
Year
1971
Tongue
English
Weight
501 KB
Volume
10
Category
Article
ISSN
0006-3525

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โœฆ Synopsis

The kinetics of rotation of the peptide (amide) bond in dimethylacetamide, glycine dimethylamide, .V-acetylsarcosine, and g1ycylsarc:osine have been studied iri basic, neutral, and acidic aqueous solutions by proton inagnet,ic resonance spectroscopy. The data indicate that the presence of nearby negative or positive charges do riot greatly perturb the energetics of conformational equilibration aboiit the amide carboii-nitrogen bond. In Ilr-acetylsarcosine and glycylsarcosine two distingriishabe ronformers are present ; their relative ahtindance is essentially 30

It is suggested that intramolec.iilar hydrogen bonding is resporisible for deviations from this popillation ratio. The activation enthalpies ( A H $ ) for rotation appear to be linearly relaied to the (:orresponding activation entropies (AS$) leading to an isokinetic temperattire of aboiit, 400ยฐK.

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