Depolarized light scattering by amides and peptides
✍ Scribed by R. T. Ingwall; P. J. Flory
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1973
- Tongue
- English
- Weight
- 663 KB
- Volume
- 12
- Category
- Article
- ISSN
- 0006-3525
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✦ Synopsis
Abstract
The Rayleigh ratios R~H~ have been measured for the depolarized scattering dilute solutions of N‐ethylacetamide (EA), N‐methylpropionamide (MP), and N‐acetyl‐pyrrolidine (AP) in P‐dioxane, and dilute aqueous solutions of N‐methylacetamide (MA), N,N‐dimethylacetamide (DMA), EA, and MP. Squares of the optical anisot‐ropies γ of the amides are obtained through extrapolation of these mesurements to infinite dilution. Values of γ^2^ found for EA and MP in dioxane are in good agreement with calculations based principally on the previously evaluated polarizability tensor of the amide group in conjunction with CC and CH bond polarizabilities. The calculations also involve averaging over all conformations, each being weighted according to the estimated conformational energy. The mean‐squared optical anisotropies (γ^2^) of the oligoglycines and oligoalanines are calculated by similarly averaging over all skeletal conformations. The anistropic polarizability tensor \documentclass{article}\pagestyle{empty}\begin{document}$ \hat \alpha $\end{document} for the prolyl structural unit
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is derived for γ^2^ for AP. The much larger optical anisotropies exhibited by the amides when dissolved in water as compared with those observed in dixane are discussed.
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