کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1164599 | 1491037 | 2013 | 11 صفحه PDF | دانلود رایگان |

• X-Pro peptides produce interconverting elution profiles on zwitterionic stationary phases.
• The cis–trans isomerization rate in solution is lower than in the chromatographic system.
• Cinchona-based zwitterionic selectors apparently lower the isomerization barrier.
• Rotamer separation is feasible <0 °C, enantiomer separation above room temperature.
The interconversion of cis and trans isomers of dipeptides containing C-terminal proline was studied by dynamic chromatography on zwitterionic chiral stationary phases at temperatures ranging from −15 °C to +45 °C The cis–trans isomers could be separated below 0 °C and above 0–10 °C plateau formation and peak coalescence phenomena occurred, which is characteristic for a dynamic process at the time-scale of partitioning. At and above room temperature, full coalescence was observed, which allowed separations of enantiomers without interference from interconversion effects. Analysis of the dynamic elution profiles of the interconverting peptides allowed the determination of isomerization rate constants and thermodynamic activation parameters (isomerization enthalpy, entropy and activation energy). In accordance with established results, isomerization rates and thermodynamic parameters were found to depend on the nature of the N-terminal amino acid. Isomerization barriers were only slightly lower than values determined with other methods but significant differences in the relative contributions of the activation enthalpy and entropy as well as isomerization rates pointed toward selector-moderated isomerization dynamics.
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Journal: Analytica Chimica Acta - Volume 795, 17 September 2013, Pages 88–98