Kinetics for the transition between cis- and trans-helices in poly-L-proline
โ Scribed by Joseph M. Rifkind
- Book ID
- 102763031
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1970
- Tongue
- English
- Weight
- 849 KB
- Volume
- 9
- Category
- Article
- ISSN
- 0006-3525
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โฆ Synopsis
Abstract
The kinetics for the cisโtrans isomerization of longโchain polyโLโproline has been studied as a function of pressure, temperature, and solvent composition in the acetic acid + nโpropanol solvent system. Our complete kinetic curves were fitted by Monte Carlo techniques, and rate constants for nucleation, growth, and termination were estimated. It was found that for the formation of a cisโhelix, high pressure, low temperature, and increased acetic acid content of the solvent, lowered the rate of nucleation relative to growth. The inverse seems to be t rue for the formation of a transโhelix. Molecular models suggest that this behavior of the kinetic constants can be due to the exposure of peptide units to solvent in the transition state for trans nucleation, and the burying of peptide units in the transition state for cis nucleation. It is further suggested from our analysis of complete kinetic curves that at least one of the assumptions usually made in the analysis of relaxation kinetics is invalid for polyโLโproline.
๐ SIMILAR VOLUMES
The synthetic polymer poly-L-proline exists in two conformational forms, I and 11, the structures of which have been elucidated by x-ray crystallography.'-3 Form I is a right-handed helix with all peptide bonds in the cis configuration, and is stable in pyridine and aliphatic alcohols. Form I1 is a
A treatment of the finite one-dimensional Ising model is given in which four possible nearest-neighbor interactions are taken into account, as well as the effect of the absence of neighbors a t the ends of the chain. This represents the most general situation possible when interactions are limited t