ISSN:
0006-3525
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Raman spectra were measured for poly(L-histidine) in H2O, poly(L-histidine-d2 and -d3) in D2O, L-histidine in H2O, L-histidine-d3 (and d4) in D2O, and 4-methylimidazole in H2O with various pH (or pD) values. The Raman scattering peaks observed for these samples were ascribed to the neutral and positively charged imidazole groups on the basis of the spectral changes due to the pH variation and to the deuterium substitution of the imino protons. The vibrational modes of these peaks were deduced from the normal coordinate analysis made on the positively charged and neutral 4-ethylimidazoles. The Raman scattering peaks from the imidazole groups in the neutral form clearly indicate that these imidazole groups exist in the equilibrium between the two tautomeric forms, the 1-N protonated from (tautomer I) and the 3-N protonated one (tautomer II). For example, the breathing vibration of the 1-N protonated form is observed at 1282 cm-1 for L-histidine and at 1304 cm-1 for 4-methylimidazole, while the breathing vibration of the 3-N protonated form is observed at 1260 cm-1 for L-histidine and 4-methylimidazole. From the temperature dependence of the relative intensities of the tautomer I peak to that of the tautomer II, it was concluded that the tautomer I is energetically more stable than the tautomer II, and the ΔH value is 1.0 ± 0.3 kcal/mol for L-histidine and 0.4 ± 0.1 kcal/mol for 4-methylimidazole. Poly(L-histidine) with the neutral imidazole side chains shows the amide I peak at 1672 cm-1, indicating that the sample assumes the antiparallel pleated-sheet structure. Poly(L-Ala75L-His25) and poly(L-Ala50L-His50) were found to take the α-helical and β-form conformations, respectively.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/bip.1979.360180804
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