Summary
The kinetics of isomerization of the helical forms of three oligoprolines was determined by far-ultraviolet CD spectropolarimetry and kinetic analysis by singular value decomposition. ZRA (Pro3-X-Pro2-Y-Pro2-Z-Pro3) and ZRA2 (Pro7-X-Pro2-Y-Pro2-Z-Pro7) bear large redox-active substituents on proline residues X, Y, and Z, but P9 (Pro9) does not. All three peptides formed a stable proline-II helix in water. In acetonitrile, both ZRA2 and P9 were converted into a proline-I helical form but ZRA remained predominantly in the proline-II helical form. Evidently, in order to undergo substantial proline II→I isomerization, an oligoproline chain containing large substituents needs to have a segment of consecutive unsubstituted proline residues that is sufficiently long to form a stable proline helix. Biexponential kinetics (A→B, k1=∼3.3×10−4s−1; B→C, k2=∼0.8×10−4s−1) were observed for the proline II→I isomerization of ZRA2 and P9 in acetonitrile and for the proline I→II isomerization of ZRA2 in water, which provides evidence for the growth and decay of a major kinetic intermediate.
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Abbreviations
- CD:
-
circular dichroism
- HPLC:
-
high-pressure liquid chromatography
- MKI:
-
major kinetic intermediate
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Slate, C.A., Binstead, R.A., Meyer, T.J. et al. Kinetics of isomerization for the proline helical forms of two oligoproline redox arrays by circular dichroic spectropolarimetry. Lett Pept Sci 6, 61–69 (1999). https://doi.org/10.1007/BF02443619
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DOI: https://doi.org/10.1007/BF02443619